U.S. patent number 8,431,252 [Application Number 13/359,810] was granted by the patent office on 2013-04-30 for anthracene derivative, and light-emitting element, light-emitting device, electronic device using anthracene derivative.
This patent grant is currently assigned to Semiconductor Energy Laboratory Co., Ltd.. The grantee listed for this patent is Masakazu Egawa, Sachiko Kawakami, Harue Nakashima, Ryoji Nomura, Tsunenori Suzuki. Invention is credited to Masakazu Egawa, Sachiko Kawakami, Harue Nakashima, Ryoji Nomura, Tsunenori Suzuki.
United States Patent |
8,431,252 |
Egawa , et al. |
April 30, 2013 |
**Please see images for:
( Certificate of Correction ) ** |
Anthracene derivative, and light-emitting element, light-emitting
device, electronic device using anthracene derivative
Abstract
An object is to provide a novel anthracene derivative. Another
object is to provide a light-emitting element with high luminous
efficiency. Yet another object is to provide a light-emitting
element with a long lifetime. Still another object is to provide a
light-emitting device and an electronic device having a long
lifetime by using the light-emitting elements of the present
invention. The anthracene derivative represented by General Formula
(1) is provided. The ability of the anthracene derivative
represented by General Formula (1) to exhibit high luminous
efficiency allows the production of a light-emitting element with
high luminous efficiency and a long lifetime.
Inventors: |
Egawa; Masakazu (Oyama,
JP), Nakashima; Harue (Kanagawa, JP),
Kawakami; Sachiko (Kanagawa, JP), Suzuki;
Tsunenori (Kanagawa, JP), Nomura; Ryoji
(Kanagawa, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Egawa; Masakazu
Nakashima; Harue
Kawakami; Sachiko
Suzuki; Tsunenori
Nomura; Ryoji |
Oyama
Kanagawa
Kanagawa
Kanagawa
Kanagawa |
N/A
N/A
N/A
N/A
N/A |
JP
JP
JP
JP
JP |
|
|
Assignee: |
Semiconductor Energy Laboratory
Co., Ltd. (JP)
|
Family
ID: |
38655460 |
Appl.
No.: |
13/359,810 |
Filed: |
January 27, 2012 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120126215 A1 |
May 24, 2012 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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12952874 |
Nov 23, 2010 |
8106392 |
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11789407 |
Nov 30, 2010 |
7842945 |
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Foreign Application Priority Data
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Apr 28, 2006 [JP] |
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2006-127118 |
Aug 30, 2006 [JP] |
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2006-233244 |
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Current U.S.
Class: |
428/690; 313/504;
548/442; 548/427; 313/506; 428/917; 257/40; 564/427 |
Current CPC
Class: |
H01L
51/0072 (20130101); H01L 51/0058 (20130101); H01L
51/0061 (20130101); H01L 51/0059 (20130101); H01L
51/006 (20130101); H05B 33/14 (20130101); C07C
211/61 (20130101); C09K 11/06 (20130101); H01L
51/0052 (20130101); C07D 209/86 (20130101); C07D
209/88 (20130101); C09K 2211/1014 (20130101); C09K
2211/1011 (20130101); H01L 2251/558 (20130101); C09K
2211/1007 (20130101); H01L 2251/552 (20130101); H01L
51/5004 (20130101); H01L 51/5012 (20130101); H01L
51/0081 (20130101); C07C 2603/24 (20170501); C09K
2211/1029 (20130101) |
Current International
Class: |
H01L
51/54 (20060101); C07D 209/56 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1 863 105 |
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Dec 2007 |
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EP |
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1 918 350 |
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May 2008 |
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EP |
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2000-68057 |
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Mar 2000 |
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JP |
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2003-146951 |
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May 2003 |
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JP |
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2003-267973 |
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Sep 2003 |
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JP |
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2003-313156 |
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Nov 2003 |
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JP |
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2004-91334 |
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Mar 2004 |
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JP |
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2004-95850 |
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Mar 2004 |
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JP |
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2004-273163 |
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Sep 2004 |
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JP |
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2005-104971 |
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Apr 2005 |
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JP |
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2005-290000 |
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Oct 2005 |
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JP |
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WO 2005/113531 |
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Dec 2005 |
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WO |
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WO 2007/102683 |
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Sep 2007 |
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WO |
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Other References
Chemical Abstract of Japanese Patent Application No. JP 2004-91334,
published Mar. 25, 2004. cited by applicant .
Search Report re European application No. EP 07742331.7, dated Feb.
14, 2012. cited by applicant .
International Search Report re application No. PCT/JP2007/058896,
dated Aug. 14, 2007. cited by applicant .
Written Opinion re application No. PCT/JP2007/058896, dated Aug.
14, 2007. cited by applicant.
|
Primary Examiner: Garrett; Dawn L.
Attorney, Agent or Firm: Husch Blackwell LLP
Parent Case Text
This application is a continuation of copending application Ser.
No. 12/952,874 filed on Nov. 23, 2010, now U.S. Pat. No. 8,106,392
which is a continuation of application Ser. No. 11/789,407 filed on
Apr. 24, 2007 (U.S. Pat. No. 7,842,945 issued Nov. 30, 2010).
Claims
The invention claimed is:
1. A light-emitting device comprising: a first electrode; a second
electrode; and a layer comprising an anthracene derivative
represented by General Formula (1), the layer being between the
first electrode and the second electrode, ##STR00159## wherein:
each of Ar.sup.1 and Ar.sup.2 represents an aryl group having 6 to
25 carbon atoms, and A is selected from General Formulae (1-1) to
(1-3): ##STR00160## each of Ar.sup.11 to Ar.sup.13 represents an
aryl group having 6 to 25 carbon atoms; .alpha. represents an
arylene group having 6 to 25 carbon atoms; Ar.sup.21 represents an
aryl group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms or an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents an aryl group having 6 to 25
carbon atoms; .beta. represents an arylene group having 6 to 25
carbon atoms; and each of R.sup.41 and R.sup.42 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms, wherein the layer is selected
from a light-emitting layer, a hole transporting layer, and a hole
injection layer.
2. The light-emitting device according to claim 1, wherein the
anthracene derivative in the light-emitting layer is a guest
material or a host material.
3. The light-emitting device according to claim 1, wherein the hole
injection layer comprises the anthracene derivative and an
inorganic compound.
4. The light-emitting device according to claim 3, wherein the
inorganic compound is an oxide of a transition metal.
5. The light-emitting device according to claim 4, wherein the
oxide of the transition metal is selected from vanadium oxide,
niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide,
tungsten oxide, manganese oxide, and rhenium oxide.
6. A lighting device comprising the light-emitting device according
to claim 1.
7. An electronic device comprising the light-emitting device
according to claim 1.
8. A light-emitting device comprising: a first electrode; a second
electrode; at least a first light-emitting unit and a second
light-emitting unit between the first electrode and the second
electrode; and a charge generation layer comprising a composite
material of an organic compound and an oxide of a transition metal
between the first light-emitting unit and the second light-emitting
unit, wherein: at least one of the first light-emitting unit and
the second light-emitting unit comprises a layer comprising an
anthracene derivative represented by General Formula (1),
##STR00161## each of Ar.sup.1 and Ar.sup.2 represents an aryl group
having 6 to 25 carbon atoms, and A is selected from General
Formulae (1-1) to (1-3): ##STR00162## each of Ar.sup.11 to
Ar.sup.13 represents an aryl group having 6 to 25 carbon atoms;
.alpha. represents an arylene group having 6 to 25 carbon atoms;
Ar.sup.21 represents an aryl group having 6 to 25 carbon atoms;
R.sup.31 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms;
R.sup.32 represents an alkyl group having 1 to 4 carbon atoms or an
aryl group having 6 to 25 carbon atoms; Ar.sup.31 represents an
aryl group having 6 to 25 carbon atoms; .beta. represents an
arylene group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms,
wherein the layer is selected from a light-emitting layer, a hole
transporting layer, and a hole injection layer.
9. The light-emitting device according to claim 8, wherein the
anthracene derivative in the light-emitting layer is a guest
material or a host material.
10. The light-emitting device according to claim 8, wherein the
hole injection layer comprises the anthracene derivative and an
inorganic compound.
11. The light-emitting device according to claim 10, wherein the
inorganic compound is an oxide of a transition metal.
12. The light-emitting device according to claim 11, wherein the
oxide of the transition metal in the hole injection layer is
selected from vanadium oxide, niobium oxide, tantalum oxide,
chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide,
and rhenium oxide.
13. The light-emitting device according to claim 8, wherein the
organic compound is selected from an aromatic amine compound, a
carbazole derivative, an aromatic hydrocarbon, and a high molecular
weight compound selected from oligomer, dendrimer, and polymer.
14. The light-emitting device according to claim 8, wherein the
oxide of the transition metal in the charge generation layer is
selected from vanadium oxide, niobium oxide, tantalum oxide,
chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide,
and rhenium oxide.
15. A lighting device comprising the light-emitting device
according to claim 8.
16. An electronic device comprising the light-emitting device
according to claim 8.
17. A light-emitting device comprising: a first electrode; a second
electrode; at least a first light-emitting unit and a second
light-emitting unit between the first electrode and the second
electrode; and a charge generation layer comprising a composite
material of an organic compound and an oxide of a transition metal
between the first light-emitting unit and the second light-emitting
unit, wherein: the first light-emitting unit comprises a first
layer, and the second light-emitting unit comprises a second layer,
each of the first layer and the second layer comprises an
anthracene derivative represented by General Formula (1),
##STR00163## each of Ar.sup.1 and Ar.sup.2 represents an aryl group
having 6 to 25 carbon atoms, and A is selected from General
Formulae (1-1) to (1-3): ##STR00164## each of Ar.sup.11 to
Ar.sup.13 represents an aryl group having 6 to 25 carbon atoms;
.alpha. represents an arylene group having 6 to 25 carbon atoms;
Ar.sup.21 represents an aryl group having 6 to 25 carbon atoms;
R.sup.31 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms;
R.sup.32 represents an alkyl group having 1 to 4 carbon atoms or an
aryl group having 6 to 25 carbon atoms; Ar.sup.31 represents an
aryl group having 6 to 25 carbon atoms; .beta. represents an
arylene group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms,
wherein each of the first layer and the second layer is selected
from a light-emitting layer, a hole transporting layer, and a hole
injection layer.
18. The light-emitting device according to claim 17, wherein the
first layer is different from the second layer.
19. The light-emitting device according to claim 18, wherein the
anthracene derivative in the light-emitting layer is a guest
material or a host material.
20. The light-emitting device according to claim 18, wherein the
hole injection layer comprises the anthracene derivative and an
inorganic compound.
21. The light-emitting device according to claim 20, wherein the
inorganic compound is an oxide of a transition metal.
22. The light-emitting device according to claim 21, wherein the
oxide of the transition metal in the hole injection layer is
selected from vanadium oxide, niobium oxide, tantalum oxide,
chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide,
and rhenium oxide.
23. The light-emitting device according to claim 17, wherein the
organic compound is selected from an aromatic amine compound, a
carbazole derivative, an aromatic hydrocarbon, and a high molecular
weight compound selected from oligomer, dendrimer, and polymer.
24. The light-emitting device according to claim 17, wherein the
oxide of the transition metal in the charge generation layer is
selected from vanadium oxide, niobium oxide, tantalum oxide,
chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide,
and rhenium oxide.
25. A lighting device comprises the light-emitting device according
to claim 17.
26. An electronic device comprising the light-emitting device
according to claim 17.
Description
TECHNICAL FIELD
The present invention relates to an anthracene derivative, and a
light-emitting element, a light-emitting device, and an electronic
device each using an anthracene derivative.
BACKGROUND ART
An organic compound can take various structures compared with an
inorganic compound, and it is possible to synthesize a material
having various functions by appropriate molecular-design of an
organic compound. Owing to these advantages, photo electronics and
electronics, which employ a functional organic material, have been
attracting attention in recent years.
A solar cell, a light-emitting element, an organic transistor, and
the like can be exemplified as an electronic device using an
organic compound as a functional organic material. These devices
take advantage of electrical properties and optical properties of
the organic compound. Among them, in particular, a light-emitting
element has been making remarkable progress.
It is considered that the light emission mechanism of a
light-emitting element is as follows: when a voltage is applied
between a pair of electrodes which interpose a light-emitting
layer, electrons injected from a cathode and holes injected from an
anode are recombined in the light-emitting layer to form a
molecular exciton, and energy is released to emit light when the
molecular exciton relaxes to the ground state. As excited states, a
singlet excited state and a triplet excited state are known, and
light emission is considered to be possible through either of these
excited states.
In an attempt to improve the performances of such a light-emitting
element, there are many problems which depend on the material, and
in order to solve these problems, improvement of the element
structure and development of a material have been carried out.
For example, in Patent Document 1: United States Patent Application
Laid-Open No. 2005-0260442, an anthracene derivative exhibiting
green light emission is disclosed. However, in Patent Document 1,
only the PL spectrum of the anthracene derivative is described, and
the device performance is not disclosed when the anthracene
derivative was applied to a light-emitting element.
Also, in Patent Document 2: Japanese Published Patent Application
No. 2004-91334, a light-emitting element using an anthracene
derivative as a charge transporting layer is mentioned. However, in
Patent Document 2, there is no description on the lifetime of the
light-emitting element.
If commercialization is considered, extending the lifetime is an
important issue. Further, the development of light-emitting
elements with much higher performances is desired.
DISCLOSURE OF INVENTION
In view of the foregoing problems, an object of the present
invention is to provide a novel anthracene derivative.
In addition, an object is to provide a light-emitting element with
high luminous efficiency as well as a light-emitting element with a
long lifetime. Another object is to provide a light-emitting,
device and an electronic device each having a long lifetime by
using these light-emitting elements.
One feature of the present invention is an anthracene derivative
represented by General Formula (1).
##STR00001##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (1-1) to (1-3). In General
Formulae (1-1) to (1-3), each of Ar.sup.11 to Ar.sup.13 represents
an aryl group having 6 to 25 carbon atoms; .alpha. represents an
arylene group having 6 to 25 carbon atoms; Ar.sup.21 represents an
aryl group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms or an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents an aryl group having 6 to 25
carbon atoms; .beta. represents an arylene group having 6 to 25
carbon atoms; and each of R.sup.41 and R.sup.42 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms.)
Another feature of the present invention is an anthracene
derivative represented by General Formula (2).
##STR00002##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (2-1) to (2-3). In General
Formulae (2-1) to (2-3), Ar.sup.11 represents an aryl group having
6 to 25 carbon atoms; each of R.sup.11 to R.sup.24 represents any
of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; each of R.sup.33 to R.sup.37
represents any of hydrogen, an alkyl group having 1 to 4 carbon
atoms, and an aryl group having 6 to 15 carbon atoms; Ar.sup.31
represents an aryl group having 6 to 25 carbon atoms; each of
R.sup.41 and R.sup.42 represents any of hydrogen, an alkyl group
having 1 to 4 carbon atoms, and an aryl group having 6 to 25 carbon
atoms; and each of R.sup.43 to R.sup.46 represents any of hydrogen,
an alkyl group having 1 to 4 carbon atoms, and an aryl group having
6 to 15 carbon atoms.)
Yet another feature of the present invention is an anthracene
derivative represented by General Formula (3).
##STR00003##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (3-1) to (3-3). In General Formulae
(3-1) to (3-3), Ar.sup.11 represents an aryl group having 6 to 25
carbon atoms; each of R.sup.25 and R.sup.26 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; Ar.sup.31 represents an aryl
group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms)
Still another feature of the present invention is an anthracene
derivative represented by General Formula (4).
##STR00004##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (4-1) to (4-3). In General Formulae
(4-1) to (4-3), Ar.sup.11 represents any of phenyl group,
1-naphthyl group, and 2-naphthyl group; each of R.sup.25 and
R.sup.26 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 15 carbon atoms;
Ar.sup.21 represents any of phenyl group, 1-naphthyl group, and
2-naphthyl group; R.sup.31 represents any of hydrogen, an alkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents any of a phenyl group,
1-naphthyl group, and 2-naphthyl group; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
In the above structure, each of Ar.sup.1 and Ar.sup.2 is preferably
a substituent represented by General Formula (11-1).
##STR00005##
(In the formula, each of R.sup.1 to R.sup.5 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 15
carbon atoms.)
In the above structure, each of Ar.sup.1 and Ar.sup.2 is preferably
a substituent represented by Structural Formula (11-2) or
(11-3).
##STR00006##
In the above structure, each of Ar1 and Ar2 is preferably a
substituent represented by General Formula (11-4).
##STR00007##
(In the formula, each of R.sup.6 and R.sup.7 represents any of an
alkyl group having 1 to 4 carbon atoms and an aryl group having 6
to 15 carbon atoms.)
In the above structure, each of Ar.sup.1 and Ar.sup.2 is preferably
a substituent represented by Structural Formula (11-5) or
(11-6).
##STR00008##
In the above structure, Ar.sup.1 and Ar.sup.2 are preferably
substituents having the same structure.
Another feature of the present invention is an anthracene
derivative represented by General Formula (5).
##STR00009##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (5-1) to (5-3). In General
Formulae (5-1) to (5-3), each of Ar.sup.11 to Ar.sup.13 represents
an aryl group having 6 to 25 carbon atoms; .alpha. represents an
arylene group having 6 to 25 carbon atoms; Ar.sup.21 represents an
aryl group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms or an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents an aryl group having 6 to 25
carbon atoms; .beta. represents an arylene group having 6 to 25
carbon atoms; and each of R.sup.41 and R.sup.42 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms.)
Further, one feature of the present invention is an anthracene
derivative represented by General Formula (6).
##STR00010##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (6-1) to (6-3). In General
Formulae (6-1) to (6-3), Ar.sup.11 represents an aryl group having
6 to 25 carbon atoms; each of R.sup.11 to R.sup.24 represents any
of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; each of R.sup.33 to R.sup.37
represents any of hydrogen, an alkyl group having 1 to 4 carbon
atoms, and an aryl group having 6 to 15 carbon atoms; Ar.sup.31
represents an aryl group having 6 to 25 carbon atoms; each of
R.sup.41 and R.sup.42 represents any of hydrogen, an alkyl group
having 1 to 4 carbon atoms, and an aryl group having 6 to 25 carbon
atoms; and each of R.sup.43 to R.sup.46 represents any of hydrogen,
an alkyl group having 1 to 4 carbon atoms, and an aryl group having
6 to 15 carbon atoms.)
Also, one feature of the present invention is an anthracene
derivative represented by General Formula (7).
##STR00011##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (7-1) to (7-3). In General Formulae
(7-1) to (7-3), Ar.sup.11 represents an aryl group having 6 to 25
carbon atoms; each of R.sup.25 and R.sup.26 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; Ar.sup.31 represents an aryl
group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
Yet another feature of the present invention is an anthracene
derivative represented by General Formula (8).
##STR00012##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (8-1) to (8-3). In General Formulae
(8-1) to (8-3), Ar.sup.11 represents any of phenyl group,
1-naphthyl group, and 2-naphthyl group; each of R.sup.25 and
R.sup.26 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 15 carbon atoms;
Ar.sup.21 represents any of phenyl group, 1-naphthyl group, and
2-naphthyl group; R.sup.31 represents any of hydrogen, an alkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents any of a phenyl group,
1-naphthyl group, and 2-naphthyl group; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
In the above structure, each of Ar.sup.1 and Ar.sup.2 is preferably
a substituent represented by General Formula (11-1).
##STR00013##
(In the formula, each of R.sup.1 to R.sup.5 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 15
carbon atoms.)
In the above structure, each of Ar.sup.1 and Ar.sup.2 is preferably
a substituent represented by Structural Formula (11-2) or
(11-3).
##STR00014##
Also, in the above structure, each of Ar.sup.1 and Ar.sup.2 is
preferably a substituent represented by General Formula (11-4).
##STR00015##
(In the formula, each of R.sup.6 and R.sup.7 represents any of an
alkyl group having 1 to 4 carbon atoms and an aryl group having 6
to 15 carbon atoms.)
Further, in the above structure, each of Ar.sup.1 and Ar.sup.2 is
preferably a substituent represented by Structural Formula (11-5)
or (11-6).
##STR00016##
Also, in the foregoing structure, Ar.sup.1 and Ar.sup.2 are
preferably substituents having the same structure.
Further, one feature of the present invention is a light-emitting
element using the foregoing anthracene derivative. Specifically,
the feature of the present invention is a light-emitting element
having the anthracene derivative between a pair of electrodes.
Another feature of the present invention is a light-emitting
element having a light-emitting layer between a pair of electrodes,
in which the light-emitting layer includes the abovementioned
anthracene derivative. It is particularly preferable to use the
abovementioned anthracene derivative as a light-emitting substance.
That is, it is preferable to have a structure in which the
anthracene derivative emits light.
The light-emitting device of the present invention has the
above-mentioned light-emitting element. The light-emitting element
comprises a layer including a light-emitting substance between a
pair of electrodes, and said layer including a light-emitting
substance comprises the foregoing anthracene derivative. The
light-emitting device of the present invention also possesses a
controller for controlling light emission of the light-emitting
element. The light-emitting device in this specification includes
an image display device, a light-emitting device, and a light
source (including a lighting device). Further, the light-emitting
device also includes a module in which a connector such as an FPC
(Flexible Printed Circuit), a TAB (Tape Automated Bonding) tape, or
a TCP (Tape Carrier Package) is attached to a panel, a module in
which a printed wiring board is provided at an end of a TAB tape or
a TCP, and a module in which an IC (Integrated Circuit) is directly
mounted on the light-emitting device by a COG (Chip On Glass)
method.
Further, an electronic device using the light-emitting element of
the present invention in its display portion is also included in
the category of the present invention. Therefore, the electronic
device of the present invention has a display portion, and the
display portion is equipped with the above-described light-emitting
element and a controller for controlling light emission of the
light-emitting element.
An anthracene derivative of the present invention has high luminous
efficiency. Therefore, by using the anthracene derivative of the
present invention in a light-emitting element, a light-emitting
element with high luminous efficiency can be obtained. Also, by
using the anthracene derivative of the present invention in a
light-emitting element, a light-emitting element with a long
lifetime can be obtained.
Further, by using an anthracene derivative of the present
invention, a light-emitting device and an electronic device each
with a long lifetime can be obtained.
BRIEF DESCRIPTION OF DRAWINGS
In the drawings:
FIGS. 1A to 1C each describe a light-emitting element of the
present invention;
FIG. 2 describes a light-emitting element of the present
invention;
FIG. 3 describes a light-emitting element of the present
invention;
FIGS. 4A and 4B describe a light-emitting device of the present
invention;
FIG. 5 describes a light-emitting device of the present
invention;
FIGS. 6A to 6D each describe an electronic device of the present
invention;
FIG. 7 describes an electronic device of the present invention;
FIG. 8 describes a lighting device of the present invention;
FIG. 9 describes a lighting device of the present invention;
FIG. 10 describes a light-emitting element of an embodiment;
FIGS. 11A and 11B each show the .sup.1H NMR chart of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA);
FIG. 12 shows the absorption spectrum of a toluene solution of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA);
FIG. 13 shows the absorption spectrum of a thin film of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA);
FIG. 14 shows the excitation spectrum and emission spectrum of a
toluene solution of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA);
FIG. 15 shows the emission spectrum of a thin film of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA);
FIGS. 16A and 16B each show the .sup.1H NMR chart of
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA);
FIGS. 17A and 17B each show the .sup.1H NMR chart of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 18 shows the absorption spectrum of a toluene solution of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 19 shows the absorption spectrum of a thin film of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9i-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 20 shows the excitation spectrum and emission spectrum of a
toluene solution of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 21 shows the emission spectrum of a thin film of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 22 shows the result of a CV measurement of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIG. 23 shows the result of a CV measurement of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA);
FIGS. 24A and 24B each show the .sup.1H NMR chart of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA);
FIG. 25 shows the absorption spectrum of a toluene solution of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA);
FIG. 26 shows the absorption spectrum of a thin film of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA);
FIG. 27 shows the emission spectrum of a toluene solution of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA);
FIG. 28 shows the emission spectrum of a thin film of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA);
FIGS. 29A and 29B each show the .sup.1H NMR chart of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIG. 30 shows the absorption spectrum of a toluene solution of
9,10-di(2-biphenyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthra-
cene (abbreviation: 2PCABPhA);
FIG. 31 shows the absorption spectrum of a thin film of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIG. 32 shows the excitation spectrum and emission spectrum of a
toluene solution of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIG. 33 shows the emission spectrum of a thin film of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIG. 34 shows the result of a CV measurement of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIG. 35 shows the result of a CV measurement of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA);
FIGS. 36A and 36B each show the .sup.1H NMR chart of
4-(carbazol-9-yl)diphenylamine (abbreviation: YGA);
FIGS. 37A and 37B each show the .sup.1H NMR chart of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA);
FIG. 38 shows the absorption spectrum of a toluene solution of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA);
FIG. 39 shows the absorption spectrum of a thin film of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA);
FIG. 40 shows the emission spectrum of a toluene solution of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA);
FIG. 41 shows the emission spectrum of a thin film of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA);
FIG. 42 shows the current density-luminance characteristic of
light-emitting element 1;
FIG. 43 shows the voltage-luminance characteristic of
light-emitting element 1;
FIG. 44 shows the luminance-current efficiency characteristic of
light-emitting element 1;
FIG. 45 shows the emission spectrum of light-emitting element
1;
FIG. 46 shows time dependence of normalized luminance of
light-emitting element 1;
FIG. 47 shows time dependence of operation voltage of
light-emitting element 1;
FIG. 48 shows the current density-luminance characteristic of
light-emitting element 2;
FIG. 49 shows the voltage-luminance characteristic of
light-emitting element 2;
FIG. 50 shows the luminance-current efficiency characteristic of
light-emitting element 2;
FIG. 51 shows the emission spectrum of light-emitting element
2;
FIG. 52 shows the current density-luminance characteristic of
light-emitting element 3;
FIG. 53 shows the voltage-luminance characteristic of
light-emitting element 3
FIG. 54 shows the luminance-current efficiency characteristic of
light-emitting element 3;
FIG. 55 shows the emission spectrum of light-emitting element
3;
FIG. 56 shows time dependence of normalized luminance of
light-emitting element 3;
FIG. 57 shows time dependence of operation voltage of
light-emitting element 3;
FIG. 58 shows the current density-luminance characteristic of
light-emitting element 4;
FIG. 59 shows the voltage-luminance characteristic of
light-emitting element 4;
FIG. 60 shows the luminance-current efficiency characteristic of
light-emitting element 4;
FIG. 61 shows the emission spectrum of light-emitting element
4;
FIG. 62 shows the current density-luminance characteristic of
light-emitting element 5;
FIG. 63 shows the voltage-luminance characteristic of
light-emitting element 5;
FIG. 64 shows the luminance-current efficiency characteristic of
light-emitting element 5;
FIG. 65 shows the emission spectrum of light-emitting element
5;
FIG. 66 shows time dependence of normalized luminance of
light-emitting element 5;
FIG. 67 shows time dependence of operation voltage of
light-emitting element 5;
FIG. 68 shows the current density-luminance characteristic of
light-emitting element 6;
FIG. 69 shows the voltage-luminance characteristic of
light-emitting element 6;
FIG. 70 shows the luminance-current efficiency characteristic of
light-emitting element 6;
FIG. 71 shows the emission spectrum of light-emitting element
6;
FIG. 72 shows the current density-luminance characteristic of
light-emitting element 7;
FIG. 73 shows the voltage-luminance characteristic of
light-emitting element 7;
FIG. 74 shows the luminance-current efficiency characteristic of
light-emitting element 7;
FIG. 75 shows the emission spectrum of light-emitting element
7;
FIG. 76 shows time dependence of normalized luminance of
light-emitting element 7;
FIG. 77 shows time dependence of operation voltage of
light-emitting element 7;
FIG. 78 shows the current density-luminance characteristic of
light-emitting element 8;
FIG. 79 shows the voltage-luminance characteristic of
light-emitting element 8;
FIG. 80 shows the luminance-current efficiency characteristic of
light-emitting element 8;
FIG. 81 shows the emission spectrum of light-emitting element
8;
FIG. 82 shows the current density-luminance characteristic of
light-emitting element 9;
FIG. 83 shows the voltage-luminance characteristic of
light-emitting element 9;
FIG. 84 shows the luminance-current efficiency characteristic of
light-emitting element 9;
FIG. 85 shows the emission spectrum of light-emitting element
9;
FIG. 86 shows the current density-luminance characteristic of
light-emitting element 10;
FIG. 87 shows the voltage-luminance characteristic of
light-emitting element 10;
FIG. 88 shows the luminance-current efficiency characteristic of
light-emitting element 10;
FIG. 89 shows the emission spectrum of light-emitting element
10;
FIGS. 90A and 90B each show the .sup.1H NMR chart of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 91 shows the absorption spectrum of a toluene solution of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 92 shows the absorption spectrum of a thin film of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 93 shows the emission spectrum of a toluene solution of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 94 shows the emission spectrum of a thin film of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 95 shows the result of a CV measurement of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIG. 96 shows the result of a CV measurement of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA);
FIGS. 97A and 97B each show the .sup.1H NMR chart of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 98 shows the absorption spectrum of a toluene solution of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 99 shows the absorption spectrum of a thin film of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 100 shows the emission spectrum of a toluene solution of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 101 shows the emission spectrum of a thin film of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 102 shows the current density-luminance characteristic of
light-emitting element 11;
FIG. 103 shows the voltage-luminance characteristic of
light-emitting element 11;
FIG. 104 shows the luminance-current efficiency characteristic of
light-emitting element 11;
FIG. 105 shows the emission spectrum of light-emitting element
11;
FIG. 106 shows the current density-luminance characteristic of
light-emitting element 12;
FIG. 107 shows the voltage-luminance characteristic of
light-emitting element 12;
FIG. 108 shows the luminance-current efficiency characteristic of
light-emitting element 12;
FIG. 109 shows the emission spectrum of a light-emitting element
12;
FIG. 110 shows the result of a CV measurement of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIG. 111 shows the result of a CV measurement of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA);
FIGS. 112A and 112B each show the .sup.1H NMR chart of
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA);
FIG. 113 shows the absorption spectrum of a toluene solution of
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA);
FIG. 114 shows the emission spectrum of a toluene solution of
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA);
FIGS. 115A and 115B each show the .sup.1H NMR chart of
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA);
FIG. 116 shows the absorption spectrum of a toluene solution of
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA);
FIG. 117 shows the emission spectrum of a toluene solution of
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA);
FIGS. 118A and 118B each show the .sup.1H NMR chart of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-
-yl)amino]anthracene (abbreviation: 2PCADFA);
FIG. 119 shows the absorption spectrum and emission spectrum of a
toluene solution of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-
-yl)amino]anthracene (abbreviation: 2PCADFA);
FIGS. 120A and 120B each show the .sup.1H NMR chart of
9,10-diphenyl-2-[N-(4'-diphenylamino-1,1'-biphenyl-4-yl)-N-phenylamino]an-
thracene (abbreviation: 2DPBAPA);
FIG. 121 shows the absorption spectrum of a toluene solution of
9,10-diphenyl-2-[N-(4'-diphenylamino-1,1'-biphenyl-4-yl)-N-phenylamino]an-
thracene (abbreviation: 2DPBAPA);
FIG. 122 shows the emission spectrum of a toluene solution of
9,10-diphenyl-2-[N-(4'-diphenylamino-1,1'-biphenyl-4-yl)-N-phenylamino]an-
thracene (abbreviation: 2DPBAPA);
FIGS. 123A and 123B each show the .sup.1H NMR chart of
2-{N-[4'-(9H-carbazol-9-yl)-1,1'-biphenyl-4-yl]-N-phenylamino}-9,10-diphe-
nylanthracene (abbreviation: 2YGBAPA);
FIG. 124 shows the absorption spectrum of a toluene solution of
2-{N-[4'-(9H-carbazol-9-yl)-1,1'-biphenyl-4-yl]-N-phenylamino}-9,10-diphe-
nylanthracene (abbreviation: 2YGBAPA);
FIG. 125 shows the emission spectrum of a toluene solution of
2-{N-[4'-(9H-carbazol-9-yl)-1,1'-biphenyl-4-yl]-N-phenylamino}-9,10-diphe-
nylanthracene (abbreviation: 2YGBAPA);
FIG. 126 shows the current density-luminance characteristic of
light-emitting element 13;
FIG. 127 shows the voltage-luminance characteristic of
light-emitting element 13;
FIG. 128 shows the luminance-current efficiency characteristic of
light-emitting element 13;
FIG. 129 shows the emission spectrum of light-emitting element
13;
FIG. 130 shows time dependence of normalized luminance of
light-emitting element 13;
FIG. 131 shows time dependence of operation voltage of
light-emitting element 13;
FIG. 132 shows the current density-luminance characteristic of
light-emitting element 14;
FIG. 133 shows the voltage-luminance characteristic of
light-emitting element 14;
FIG. 134 shows the luminance-current efficiency characteristic of
light-emitting element 14;
FIG. 135 shows the emission spectrum of light-emitting element
14;
FIG. 136 shows time dependence of normalized luminance of
light-emitting element 14;
FIG. 137 shows time dependence of operation voltage of
light-emitting element 14;
FIG. 138 shows the current density-luminance characteristic of
light-emitting element 15;
FIG. 139 shows the voltage-luminance characteristic of
light-emitting element 15;
FIG. 140 shows the luminance-current efficiency characteristic of
light-emitting element 15; and
FIG. 141 shows the emission spectrum of light-emitting element
15.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiment modes and embodiments of the present
invention will be explained with reference to the accompanied
drawings. However, the present invention is not limited to the
following description, and it is easily understood by those skilled
in the art that the modes and details thereof can be changed in
various ways without departing from the concept and scope of the
present invention. Therefore, the present invention is not
interpreted limited to the following description of embodiment
modes and embodiments.
Embodiment Mode 1
In this embodiment mode, an anthracene derivative of the present
invention is described.
The anthracene derivative of the present invention is the
anthracene derivative represented by General Formula (1).
##STR00017##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (1-1) to (1-3). In General
Formulae (1-1) to (1-3), each of Ar.sup.11 to Ar.sup.13 represents
an aryl group having 6 to 25 carbon atoms; .alpha. represents an
arylene group having 6 to 25 carbon atoms; Ar.sup.21 represents an
aryl group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms or an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents an aryl group having 6 to 25
carbon atoms; .beta. represents an arylene group having 6 to 25
carbon atoms; and each of R.sup.41 and R.sup.42 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms.)
In General Formula (1), a substituent represented by Structural
Formulae (20-1) to (20-9) can be given as a substituent represented
by each of Ar.sup.1 and Ar.sup.2, for example.
##STR00018## ##STR00019##
In General Formula (1-1), a substituent represented by Structural
Formulae (21-1) to (21-9) can be given as a substituent represented
by each of Ar.sup.11 to Ar.sup.13, for example.
##STR00020## ##STR00021##
Also, in General Formula (1-1), a substituent represented by
Structural Formulae (22-1) to (22-9) can be given as a substituent
represented by .alpha., for example.
##STR00022## ##STR00023##
Consequently, a substituent represented by Structural Formulae
(31-1) to (31-23) can be given as a substituent represented by
General Formula (1-1), for example.
##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028##
##STR00029## ##STR00030##
Further, in General Formula (1-2), a substituent represented by
Structural Formulae (23-1) to (23-9) can be given as a substituent
represented by Ar.sup.21, for example.
##STR00031## ##STR00032##
Furthermore, in General Formula (1-2), Structural Formulae (24-1)
to (24-18) can be given as specific examples of R.sup.31, for
example.
##STR00033## ##STR00034##
Also, in General Formula (1-2), Structural Formulae (25-1) to
(25-17) can be given as specific examples of R.sup.32, for
example.
##STR00035## ##STR00036##
Consequently, Structural Formulae (32-1) to (32-42) can be given as
specific examples of General Formula (1-2), for example.
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048##
Also, in General Formula (1-3), Structural Formulae (26-1) to
(26-9) can be given as specific examples of Ar.sup.31, for
example.
##STR00049## ##STR00050##
Also, in General Formula (1-3), Structural Formulae (27-1) to
(27-9) can be given as specific examples of .beta., for
example.
##STR00051## ##STR00052##
Further, in General Formula (1-3), Structural Formulae (28-1) to
(28-18) can be given as specific examples of each of R.sup.41 and
R.sup.42, for example.
##STR00053## ##STR00054##
Consequently, Structural Formulae (33-1) to (33-34) can be given as
specific examples of General Formula (1-3), for example.
##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059##
##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064##
##STR00065##
Also, among anthracene derivatives represented by General Formula
(1), the anthracene derivative represented by General Formula (2)
is preferable.
##STR00066##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (2-1) to (2-3). In General
Formulae (2-1) to (2-3), Ar.sup.11 represents an aryl group having
6 to 25 carbon atoms; each of R.sup.11 to R.sup.24 represents any
of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; each of R.sup.33 to R.sup.37
represents any of hydrogen, an alkyl group having 1 to 4 carbon
atoms, and an aryl group having 6 to 15 carbon atoms; Ar.sup.31
represents an aryl group having 6 to 25 carbon atoms; each of
R.sup.41 and R.sup.42 represents any of hydrogen, an alkyl group
having 1 to 4 carbon atoms, and an aryl group having 6 to 25 carbon
atoms; and each of R.sup.43 to R.sup.46 represents any of hydrogen,
an alkyl group having 1 to 4 carbon atoms, and an aryl group having
6 to 15 carbon atoms.)
Also, among anthracene derivatives represented by General Formula
(1), the anthracene derivative represented by General Formula (3)
is preferable.
##STR00067##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (3-1) to (3-3). In General Formulae
(3-1) to (3-3), Ar.sup.11 represents an aryl group having 6 to 25
carbon atoms; each of R.sup.25 and R.sup.26 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; Ar.sup.31 represents an aryl
group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
Also, among anthracene derivatives represented by General Formula
(1), the anthracene derivative represented by General Formula (4)
is preferable.
##STR00068##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (4-1) to (4-3). In General Formulae
(4-1) to (4-3), Ar.sup.11 represents any of a phenyl group, a
1-naphthyl group, and a 2-naphthyl group; each of R.sup.25 and
R.sup.26 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 15 carbon atoms;
Ar.sup.21 represents any of phenyl group, 1-naphthyl group, and
2-naphthyl group; R.sup.31 represents any of hydrogen, an alkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents any of a phenyl group, a
1-naphthyl group, and a 2-naphthyl group; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
In foregoing General Formulae (1) to (4), each of Ar.sup.1 and
Ar.sup.2 is preferably a substituent represented by General Formula
(11-1).
##STR00069##
(In the formula, each of R.sup.1 to R.sup.5 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 15
carbon atoms.)
Also, in foregoing General Formulae (1) to (4), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by Structural
Formula (11-2) or (11-3).
##STR00070##
Further, in foregoing General Formulae (1) to (4), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by General
Formula (11-4).
##STR00071##
(In the formula, each of R.sup.6 and R.sup.7 represents an alkyl
group having 1 to 4 carbon atoms.)
Also, in foregoing General Formulae (1) to (4), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by Structural
Formula (11-5) or (11-6).
##STR00072##
Further, in foregoing General Formulae (1) to (4), Ar.sup.1 and
Ar.sup.2 are preferably substituents having the same structure.
Furthermore, in foregoing General Formulae (1) to (4), A preferably
bonds at the 2-position of the anthracene skeleton. By bonding at
the 2-position, steric hindrance with each of Ar.sup.1 and Ar.sup.2
is reduced.
That is, a preferable anthracene derivative is represented by
General Formula (5).
##STR00073##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (5-1) to (5-3). In General Formulae
(5-1) to (5-3), each of Ar.sup.11 to Ar.sup.13 represents an aryl
group having 6 to 25 carbon atoms; .alpha. represents an arylene
group having 6 to 25 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms or an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents an aryl group having 6 to 25
carbon atoms; .beta. represents an arylene group having 6 to 25
carbon atoms; and each of R.sup.41 and R.sup.42 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms.)
Also, a preferable anthracene derivative is exemplified by General
Formula (6).
##STR00074##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents a substituent
represented by any of General Formulae (6-1) to (6-3). In General
Formulae (6-1) to (6-3), Ar.sup.11 represents an aryl group having
6 to 25 carbon atoms; each of R.sup.11 to R.sup.24 represents any
of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; each of R.sup.33 to R.sup.37
represents any of hydrogen, an alkyl group having 1 to 4 carbon
atoms, and an aryl group having 6 to 15 carbon atoms; Ar.sup.31
represents an aryl group having 6 to 25 carbon atoms; each of
R.sup.41 and R.sup.42 represents any of hydrogen, an alkyl group
having 1 to 4 carbon atoms, and an aryl group having 6 to 25 carbon
atoms; and each of R.sup.43 to R.sup.46 represents any of hydrogen,
an alkyl group having 1 to 4 carbon atoms, and an aryl group having
6 to 15 carbon atoms.)
Further, the anthracene derivative represented by General Formula
(7) is preferable.
##STR00075##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (7-1) to (7-3). In General Formulae
(7-1) to (7-3), Ar.sup.11 represents an aryl group having 6 to 25
carbon atoms; each of R.sup.25 and R.sup.26 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 15 carbon atoms; Ar.sup.21 represents an aryl
group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; Ar.sup.31 represents an aryl
group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
Furthermore, preferable example for the anthracene derivative is
represented by General Formula (8).
##STR00076##
(In the formula, each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms, and A represents any substituent
represented by General Formulae (8-1) to (8-3). In General Formulae
(8-1) to (8-3), Ar.sup.11 represents any of phenyl group,
1-naphthyl group, and 2-naphthyl group; each of R.sup.25 and
R.sup.26 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 15 carbon atoms;
Ar.sup.21 represents any of phenyl group, 1-naphthyl group, and
2-naphthyl group; R.sup.31 represents any of hydrogen, an alkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 25
carbon atoms; Ar.sup.31 represents any of a phenyl group, a
1-naphthyl group, and a 2-naphthyl group; and each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms.)
In foregoing General Formulae (5) to (8), each of Ar.sup.1 and
Ar.sup.2 is preferably a substituent represented by General Formula
(11-1).
##STR00077##
(In the formula, each of R.sup.1 to R.sup.5 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl
group having 1 to 4 carbon atoms, and an aryl group having 6 to 15
carbon atoms.)
Also, in foregoing General Formulae (5) to (8), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by Structural
Formula (11-2) or (11-3).
##STR00078##
Further, in foregoing General Formulae (5) to (8), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by General
Formula (11-4).
##STR00079##
(In the formula, each of R.sup.6 and R.sup.7 represents an alkyl
group having 1 to 4 carbon atoms.)
Also, in foregoing General Formulae (5) to (8), each of Ar.sup.1
and Ar.sup.2 is preferably a substituent represented by General
Formula (11-5) or (11-6).
##STR00080##
Further, in foregoing General Formulae (5) to (8), Ar.sup.1 and
Ar.sup.2 are preferably substituents having the same structure.
As specific examples of the anthracene derivative represented by
General Formula (1), the anthracene derivatives represented by
Structural Formulae (101) to (118), Structural Formulae (201) to
(218), and Structural Formulae (301) to (318) can be given.
However, the present invention is not limited thereto.
##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085##
##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090##
##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095##
##STR00096## ##STR00097## ##STR00098## ##STR00099##
##STR00100##
The anthracene derivatives represented by Structural Formulae (101)
to (118) are specific examples of General Formula (1) in the case
where A is General Formula (1-1), and the anthracene derivatives
represented by Structural Formulae (201) to (218) are specific
examples of General Formula (1) in the case where A is General
Formula (1-2). Also, the anthracene derivatives represented by
Structural Formulae (301) to (318) are specific examples of General
Formula (1) in the case where A is General Formula (1-3).
A variety of reactions can be applied as a synthetic method of an
anthracene derivative of the present invention. For example, the
anthracene derivative of the present invention can be synthesized
by conducting the synthesis reactions shown in following Reaction
Schemes (A-1) to (A-5) and (B-1) to (B-3).
##STR00101##
A compound including carbazole in a skeleton (Compound A) is
reacted with a halogen or halide such as N-bromosuccinimide (NBS),
N-iodosuccinimide (NIS), bromine (Br.sub.2), potassium iodide (KI),
or iodine (I.sub.2) to synthesize a compound including
3-halogenated carbazole in a skeleton (Compound B), and then
subjected to a coupling reaction with arylamine using a metal
catalyst such as a palladium catalyst (Pd catalyst), thereby
obtaining a compound C. In the synthetic scheme (A-1), a halogen
element (X) is preferably iodine or bromine R.sup.31 represents any
of hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms. R.sup.32 represents an alkyl
group having 1 to 4 carbon atoms, or an aryl group having 6 to 25
carbon atoms. Further, Ar.sup.11 represents an aryl group having 6
to 25 carbon atoms.
##STR00102##
A compound including carbazole in a skeleton (Compound D) is
reacted with a dihalide of an aromatic compound to synthesize a
compound including N-(aryl halide)carbazole in a skeleton (Compound
E), and Compound E is subjected to a coupling reaction with
arylamine using a metal catalyst such as palladium, thereby
obtaining Compound F. In the synthetic scheme (A-2), a halogen
element (X.sub.1 and X.sub.2) of the dihalide of an aromatic
compound is preferably iodine or bromine. X.sub.1 and X.sub.2 may
be the same or different from each other. Each of R.sup.41 and
R.sup.42 represents any of hydrogen, an alkyl group having 1 to 4
carbon atoms, and an aryl group having 6 to 25 carbon atoms. .beta.
represents an arylene group having 6 to 25 carbon atoms. Ar.sup.31
represents an aryl group having 6 to 25 carbon atoms.
##STR00103##
##STR00104##
##STR00105##
A halide of anthraquinone (Compound H) is synthesized by the
Sandmyer reaction of 1-aminoanthraquinone or 2-aminoanthraquinone
(Compound G). The halide of anthraquinone (Compound H) is reacted
with aryllithium to synthesize a diol of a 9,10-dihydroanthracene
derivative (Compound I). Then, the diol of the
9,10-dihydroanthracene derivative (Compound I) is subjected to
dehydroxylation using sodium phosphinate monohydrate, potassium
iodide in acetic acid, which allows the formulation of
9,10-diarylanthracene halide (Compound J).
Note that in each of Synthetic Schemes (A-3) to (A-5), X represents
a halogen element. Also, each of Ar.sup.1 and Ar.sup.2 represents
an aryl group having 6 to 25 carbon atoms.
##STR00106##
An anthracene derivative of the present invention can be
synthesized by the reaction shown in Synthetic Scheme (B-1) using
Compound J prepared in Synthetic Scheme (A-5). By the coupling
reaction of Compound J with an arylamine using a metal catalyst
such as a palladium catalyst, the anthracene derivative of the
present invention represented by General Formula (1-1a) can be
synthesized. In Synthetic Scheme (B-1), each of Ar.sup.1 and
Ar.sup.2 represents an aryl group having 6 to 25 carbon atoms, each
of Ar.sup.11 to Ar.sup.13 represents an aryl group having 6 to 25
carbon atoms, and .alpha. represents an arylene group having 6 to
25 carbon atoms. Note that the compound represented by General
Formula (1-1a) corresponds to the case where A in General Formula
(1) is General Formula (1-1).
##STR00107##
An anthracene derivative of the present invention can be
synthesized by a reaction shown in Synthetic Scheme (B-2), using
Compound C prepared according to Synthetic Scheme (A-1) and
Compound J provided by Synthetic Scheme (A-5). The coupling
reaction between Compound C and Compound J using a metal catalyst
such as a palladium catalyst gives the anthracene derivative of the
present invention represented by General Formula (1-2a). In
Synthetic Scheme (B-2), each of Ar.sup.1 and Ar.sup.2 represents an
aryl group having 6 to 25 carbon atoms; Ar.sup.21 represents an
aryl group having 6 to 25 carbon atoms; R.sup.31 represents any of
hydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl
group having 6 to 25 carbon atoms; and R.sup.32 represents either
of an alkyl group having 1 to 4 carbon atoms and an aryl group
having 6 to 25 carbon atoms. Note that the compound represented by
General Formula (1-2a) corresponds to the case where A in foregoing
General Formula (1) is General Formula (1-2).
##STR00108##
An anthracene derivative of the present invention can be
synthesized by a reaction shown in Synthetic Scheme (B-3), using
Compound F formed in Synthetic Scheme (A-2) and Compound J prepared
by Synthetic Scheme (A-5). The coupling reaction between Compound F
and Compound J using a metal catalyst such as a palladium catalyst
leads to the formation of the anthracene derivative of the present
invention represented by General Formula (1-3a). In Synthetic
Scheme (B-3), each of Ar.sup.1 and Ar.sup.2 represents an aryl
group having 6 to 25 carbon atoms; Ar.sup.31 represents an aryl
group having 6 to 25 carbon atoms; .beta. represents an arylene
group having 6 to 25 carbon atoms; and each of R.sup.41 and
R.sup.42 represents hydrogen, an alkyl group having 1 to 4 carbon
atoms, and an aryl group having 6 to 25 carbon atoms. Note that the
compound represented by General Formula (1-3a) corresponds to the
case where A in foregoing General Formula (1) is General Formula
(1-3).
An anthracene derivative of the present invention has high luminous
quantum yield, and emits blue green to yellow green light.
Therefore, the anthracene derivative of the present invention can
be favorably used for a light-emitting element.
Also, since the anthracene derivatives of the present invention are
capable of green light emission with high efficiency, they can be
favorably used for a full-color display. Further, the ability of
the anthracene derivative of the present invention to achieve green
light emission with a long lifetime allows their application in a
full-color display.
Furthermore, since the anthracene derivative of the present
invention can provide green light emission with high efficiency,
white light emission can be obtained by combining with another
light emissive material. For example, in an attempt to realize
white light emission using red (R), green (G), and blue (B)
emissions which exhibit the corresponding NTSC chromaticity
coordinates, white color cannot be obtained unless light emissions
of these colors are mixed with a proportion of approximately red
(R):green (G):blue (B)=1:6:3. That is, green light emission with
high luminance is necessary, and, therefore, the anthracene
derivative of the present invention by which green light emission
with high efficiency can be obtained is favorable for a
light-emitting device.
Also, in the anthracene derivative of the present invention, only
one substituent A is bonded to an anthracene skeleton as
represented by General Formula (1). Consequently, compared with a
disubstituted compound in which two A units are bonded to the
anthrace skeleton, the anthracene derivative of the present
invention is possible to exhibit light emission with a short
wavelength. Further, since the molecular weight of the
disubstituted compound is very high, film formation by an
evapolariton method is difficult; however, film formation by an
evaporation method is possible with the anthracene derivative of
the present invention. In addition, synthesis of a disubstituted
compound requires higher cost than that of the anthracene
derivative of the present invention which is monosubstituted.
Further, the inventors found that, when the anthracene derivatives
are applied to a light-emitting element, the use of the
monosubstituted anthracene derivative provides a longer lifetime
than that of the disubstituted one. Consequently, by applying the
anthracene derivative of the present invention to a light-emitting
element, a light-emitting element with a long lifetime can be
obtained.
Furthermore, the anthracene derivative of the present invention is
stable even if they are subjected to the oxidation-reduction cycle
repeatedly. Consequently, by using the anthracene derivative of the
present invention in a light-emitting element, a light-emitting
element with a long lifetime can be obtained.
Embodiment Mode 2
One mode of a light-emitting element using an anthracene derivative
of the present invention is described below with reference to FIG.
1A.
A light-emitting element of the present invention has a plurality
of layers between a pair of electrodes. The plurality of layers are
a combination of layers formed of a substance having a high carrier
injecting property and a substance having a high carrier
transporting property which are stacked so that a light-emitting
region is formed in a region away from the electrodes, that is,
recombination of carriers is performed in an area away from the
electrodes.
In this embodiment mode, a light-emitting element includes a first
electrode 102, a first layer 103, a second layer 104, a third layer
105, and a fourth layer 106 which are sequentially stacked over the
first electrode 102, and a second electrode 107 provided thereover.
It is to be noted that description will be made below in this
embodiment mode with an assumption that the first electrode 102
functions as an anode and the second electrode 107 functions as a
cathode.
A substrate 101 is used as a support of the light-emitting element.
For the substrate 101, glass, plastic, or the like can be used for
example. It is to be noted that another material may be used as
long as it functions as a support in a manufacturing process of the
light-emitting element.
As the first electrode 102, a metal, an alloy, an electrically
conductive compound, a mixture thereof, or the like having a high
work function (specifically, 4.0 eV or more) is preferably used.
Specifically, indium oxide-tin oxide (ITO: Indium Tin Oxide),
indium oxide-tin oxide including silicon or silicon oxide, indium
oxide-zinc oxide (IZO: Indium Zinc Oxide), indium oxide including
tungsten oxide and zinc oxide (IWZO), or the like is represented.
Although these conductive metal oxide films are generally formed by
sputtering, they may be formed by applying a sol-gel method or the
like. For example, a film of indium oxide-zinc oxide (IZO) can be
formed by a sputtering method using a target in which 1 to 20 wt %
of zinc oxide is added to indium oxide. A film of indium oxide
including tungsten oxide and zinc oxide (IWZO) can be formed by a
sputtering method using a target in which 0.5 to 5 wt % of tungsten
oxide and 0.1 to 1 wt % of zinc oxide are included in indium oxide.
In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W),
chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper
(Cu), palladium (Pd), a nitride of a metal (such as titanium
nitride: TiN), or the like is exemplified.
The first layer 103 is a layer including a substance having a high
hole injecting property. Molybdenum oxide (MoOx), vanadium oxide
(VOx), ruthenium oxide (RuOx), tungsten oxide (WOx), manganese
oxide (MnOx), or the like can be used. Alternatively, the first
layer 103 can be formed using phthalocyanine (abbreviation:
H.sub.2Pc); a phthalocyanine-based compound such as copper
phthalocyanine (CuPc); an aromatic amine compound such as
4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl
(abbreviation: DPAB) or
4,4'-bis(N-{-4-[N-(3-methylphenyl)-N-phenylamino]phenyl}-N-phenylamino)bi-
phenyl (abbreviation: DNTPD); or a high molecular weight material
such as poly(ethylene dioxythiophene)/poly(styrenesulfonic acid)
(PEDOT/PSS), or the like.
Alternatively, a composite material formed by composing an organic
compound and an inorganic compound can be used for the first layer
103. In particular, a composite material including an organic
compound and an inorganic compound having an electron accepting
property with respect to the organic compound has an excellent hole
injecting property and hole transporting property because the
electron transfer takes place between the organic compound and the
inorganic compound, increasing the carrier density.
In a case of using a composite material formed by mixing an organic
compound and an inorganic compound for the first layer 103, the
first layer 103 can achieve an ohmic contact with the first
electrode 102; therefore, a material of the first electrode can be
selected regardless of work function.
As the inorganic compound used for the composite material, an oxide
of a transition metal is preferably used. For example, oxides of
metals belonging to Groups 4 to 8 in the periodic table can be
given. Specifically, it is preferable to use vanadium oxide,
niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide,
tungsten oxide, manganese oxide, and rhenium oxide because of their
high electron accepting properties. Among them, molybdenum oxide is
particularly preferable because it is stable under air, has a low
moisture absorption property, and is easily handled.
As the organic compound used for the composite material, various
compounds such as an aromatic amine compound, a carbazole
derivative, an aromatic hydrocarbon, and a high molecular weight
compound (such as oligomer, dendrimer, or polymer) can be used. The
organic compound used for the composite material is preferably an
organic compound having a high hole transporting property.
Specifically, a substance having a hole mobility of greater than or
equal to 10.sup.-6 cm.sup.2/Vs is preferably used. However, other
materials than these materials may also be used as long as the hole
transporting properties thereof are higher than the electron
transporting properties thereof. The organic compounds which can be
used for the composite material will be specifically shown
below.
For example, the following can be represented as the aromatic amine
compound: N,N'-di(p-tolyl)-N,N'-diphenyl-p-phenylenediamine
(abbreviation: DTDPPA);
4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl
(abbreviation: DPAB);
4,4'-bis(N-{4-[N'-(3-methylphenyl)-N'-phenylamino]phenyl}-N-phenyl-
amino)biphenyl (abbreviation: DNTPD);
1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene
(abbreviation: DPA3B); and the like.
As the carbazole derivatives which can be used for the composite
material, the following can be provided specifically:
3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole
(abbreviation: PCzPCA1);
3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole
(abbreviation: PCzPCA2);
3-[N-(1-naphtyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole
(abbreviation: PCzPCN1); and the like.
Moreover, as the carbazole derivative which can be used for the
composite material, the following can be given:
4,4'-di(N-carbazolyl)biphenyl (abbreviation: CBP);
1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB);
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation:
CzPA); 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene;
or the like.
As the aromatic hydrocarbon which can be used for the composite
material, the following can be given for example:
2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA);
2-tert-butyl-9,10-di(1-naphthyl)anthracene;
9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA);
2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation:
t-BuDBA); 9,10-di(2-naphthyl)anthracene (abbreviation: DNA);
9,10-diphenylanthracene (abbreviation: DPAnth);
2-tert-butylanthracene (abbreviation: t-BuAnth);
9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA);
2-tert-butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene;
9,10-bis[2-(1-naphthyl)phenyl]anthracene;
2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene;
2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene; 9,9'-bianthryl;
10,10'-diphenyl-9,9'-bianthryl;
10,10'-bis(2-phenylphenyl)-9,9'-bianthryl;
10,10'-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-bianthryl;
anthracene; tetracene; rubrene; perylene;
2,5,8,11-tetra(tert-butyl)perylene; and the like. Besides these
compounds, pentacene, coronene, or the like can also be used. In
particular, an aromatic hydrocarbon which has a hole mobility of
greater than or equal to 1.times.10.sup.-6 cm.sup.2/Vs and which
has 14 to 42 carbon atoms is more preferable.
The aromatic hydrocarbon which can be used for the composite
material may have a vinyl moiety. As the aromatic hydrocarbon
having a vinyl group, the following are given for example:
4,4'-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi);
9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (abbreviation:
DPVPA); and the like.
Moreover, a high molecular weight compound such as
poly(N-vinylcarbazole) (abbreviation: PVK) or
poly(4-vinyltriphenylamine) (abbreviation: PVTPA) can also be
used.
As a substance forming the second layer 104, a substance having a
high hole transporting property, specifically, an aromatic amine
compound (that is, a compound having a benzene ring-nitrogen bond)
is preferable. As a material that is widely used,
4,4'-bis[N-(3-methylphenyl)-N-phenylamino]biphenyl, derivatives
thereof such as 4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl
(hereinafter referred to as NPB), and star burst aromatic amine
compounds such as 4,4',4''-tris(N,N-diphenyl-amino)triphenylamine,
and 4,4',4''-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine
can be given. These materials described here mainly are substances
each having a hole mobility of greater than or equal to 10.sup.-6
cm.sup.2/Vs. However, other materials than these compounds may also
be used as long as the hole transporting properties thereof are
higher than the electron transporting properties. The second layer
104 is not limited to a single layer, and a mixed layer of the
aforementioned substances, or a stacked layer which comprises two
or more layers each including the aforementioned substance may be
used.
The third layer 105 is a layer including a light-emitting
substance. In this embodiment mode, the third layer 105 includes
the anthracene derivative of the present invention described in
Embodiment Mode 1. The anthracene derivative of the present
invention can favorably be applied to a light-emitting element as a
light-emitting substance since the anthracene derivative of the
present invention exhibits light emission of blue green to yellow
green.
As the fourth layer 106, a substance having a high electron
transporting property can be used. For example, a layer including a
metal complex or the like having a quinoline or benzoquinoline
moiety, such as tris(8-quinolinolato)aluminum (abbreviation: Alq),
tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq.sub.3),
bis(10-hydroxybenzo[h]quinolinato)beryllium (abbreviation:
BeBq.sub.2), or
bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum
(abbreviation: BAlq) can be used. Alternatively, a metal complex or
the like having an oxazole-based or thiazole-based ligand, such as
bis[2-(2-hydroxyphenyl)benzoxazolato]zinc (abbreviation:
Zn(BOX).sub.2) or bis[2-(2-hydroxyphenyl)-benzothiazolato]zinc
(abbreviation: Zn(BTZ).sub.2) can be used. Besides the metal
complexes, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole
(abbreviation: PBD),
1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene
(abbreviation: OXD-7),
3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole
(abbreviation: TAZ), bathophenanthroline (abbreviation: BPhen),
bathocuproine (abbreviation: BCP), or the like can also be used.
The substances described here mainly are substances each having an
electron mobility of greater than or equal to 10.sup.-6
cm.sup.2/Vs. The electron transporting layer may be formed using
other materials than those described above as long as the materials
have higher electron transporting properties than hole transporting
properties. Furthermore, the electron transporting layer is not
limited to a single layer, and two or more layers in which each
layer is made of the aforementioned material may be stacked.
As a substance fowling the second electrode 107, a metal, an alloy,
an electrically conductive compound, a mixture thereof, or the like
having a low work function (specifically, 3.8 eV or less) is
preferably used. As a specific example of such a cathode material,
an element belonging to Group 1 or Group 2 in the periodic table,
that is, an alkali metal such as lithium (Li) or cesium (Cs), an
alkaline earth metal such as magnesium (Mg), calcium (Ca), or
strontium (Sr), an alloy including these metals (MgAg, AlLi) can be
employed. A rare earth metal such as europium (Eu) or ytterbium
(Yb), an alloy including these rare earth metals, or the like is
also suitable. However, by providing a layer having a function to
promote electron injection from the second electrode 107 to the
fourth layer 106, various conductive materials such as Al, Ag, ITO,
or ITO including silicon or silicon oxide can be used for the
second electrode 107 regardless of the magnitude of the work
function.
As the layer having a function of promoting electron injection, an
alkali metal, an alkaline earth metal, or a compound thereof such
as lithium fluoride (LiF), cesium fluoride (CsF), or calcium
fluoride (CaF.sub.2) can be used. Alternatively, a layer which
contains substance having an electron transporting property and an
alkali metal, an alkaline earth metal, or a compound thereof (Alq
including magnesium (Mg) for example) can be used. It is preferable
to use such a layer since electron injection from the second
electrode 107 proceeds efficiently.
Various methods can be used for forming the first layer 103, the
second layer 104, the third layer 105, and the fourth layer 106.
For example, an evaporation method, an ink-jet method, a spin
coating method, or the like may be used. Furthermore, each
electrode or each layer may be formed by a different film formation
method.
By applying voltage between the first electrode 102 and the second
electrode 107, holes and electrons are recombined in the third
layer 105 including a substance with a high light-emitting
property, which results in a light-emission from the light-emitting
element of the present invention. That is, the light-emitting
element of the present invention has a structure in which a
light-emitting region is formed in the third layer 105.
Light emission is extracted outside through one or both of the
first electrode 102 and the second electrode 107. Therefore, one or
both of the first electrode 102 and the second electrode 107 is/are
formed using an electrode having a light transmitting property. In
a case where only the first electrode 102 has a light transmitting
property, light emission is extracted from a substrate side through
the first electrode 102 as shown in FIG. 1A. Alternatively, in a
case where only the second electrode 107 is formed using the
electrode having a light transmitting property, light emission is
extracted from the side opposite to the substrate through the
second electrode 107 as shown in FIG. 1B. In a case where each of
the first electrode 102 and the second electrode 107 is the
electrode having a light transmitting property, light emission is
extracted from both of the substrate side and the side opposite to
the substrate through the first electrode 102 and the second
electrode 107, as shown in FIG. 1C.
A structure of layers provided between the first electrode 102 and
the second electrode 107 is not limited to the above-described
structure. A structure other than the above-described structure may
be used as long as the light-emitting region, in which holes and
electrons are recombined, is located away from the first electrode
102 and the second electrode 107, which permits preventing the
quenching phenomenon promoted by the electrodes.
In other words, a stacked structure of the layer is not strictly
limited to the abovementioned structure, and a layer formed using a
substance having a high electron transporting property, a substance
having a high hole transporting property, a substance having a high
electron injecting property, a substance having a high hole
injecting property, a bipolar substance (substance having a high
electron transporting property and a high hole transporting
property), a hole blocking material, or the like may be freely
combined with the anthracene derivative of the present
invention.
A light-emitting element shown in FIG. 2 has a structure in which a
first electrode 302 serving as a cathode, a first layer 303 formed
using a substance having a high electron transporting property, a
second layer 304 including a light-emitting substance, a third
layer 305 formed using a substance having a high hole transporting
property, a fourth layer 306 formed using a substance having a high
hole injecting property, and a second electrode 307 serving as an
anode are sequentially stacked over a substrate 301.
In this embodiment mode, a light-emitting element is fabricated
over a substrate made of glass, plastic, or the like. By
fabricating a plurality of the light-emitting elements described
above over one substrate, a passive-type light-emitting device can
be manufactured. Alternatively, for example, a thin film transistor
(TFT) may be formed over a substrate made of glass, plastic, or the
like, and the light-emitting elements may be manufactured over an
electrode electrically connected to the TFT. Accordingly, an active
matrix light-emitting device can be manufactured, in which driving
of the light-emitting element is controlled by the TFT. The
structure of the TFT is not strictly limited, and the TFT may be a
staggered TFT or an inverted staggered TFT. Crystallinity of a
semiconductor used for the TFT is also not limited, and an
amorphous semiconductor or a crystalline semiconductor may be used.
In addition, a driving circuit formed over a TFT substrate may be
formed using an N-type TFT and a P-type TFT, or may be formed using
any one of an N-type TFT and a P-type TFT.
As shown in this embodiment mode, an anthracene derivative of the
present invention can be used for a light-emitting layer without
adding any other light-emitting substance, since said anthracene
derivative exhibits light emission of blue green to yellow
green.
Since the anthracene derivative of the present invention has high
luminous efficiency, a light-emitting element with high luminous
efficiency can be obtained by using the anthracene derivative of
the present invention in a light-emitting element. Also, by using
the anthracene derivative of the present invention in a
light-emitting element, a light-emitting element with a long
lifetime can be obtained.
Because anthracene derivatives of the present invention are capable
of green light emission with high efficiency, they can be favorably
used for a full-color display. Further, the ability of the
anthracene derivative of the present invention to achieve green
light emission with a long lifetime allows their application in a
full-color display.
Furthermore, since the light-emitting element using the anthracene
derivative of the present invention is capable of green light
emission with high efficiency, white light emission can be obtained
by combining with another light emission material. For example, in
an attempt to realize white light emission using red (R), green
(G), and blue (B) emissions which exhibit the corresponding NTSC
chromaticity coordinates, white color cannot be obtained unless
light emissions of these colors are mixed with a proportion of
approximately red (R):green (G):blue (B)=1:6:3. That is, green
light emission with high luminance is necessary, and, therefore,
the anthracene derivative of the present invention by which green
light emission with high efficiency can be obtained is favorable
for a light-emitting device.
Embodiment Mode 3
In this embodiment mode, a light-emitting element having a
different structure from that described in Embodiment Mode 2 will
be explained.
In this embodiment mode, the third layer 105 shown in FIGS. 1A to
1C is formed by dispersing an anthracene derivative of the present
invention into another substance, whereby light emission can be
obtained from the anthracene derivative of the present invention.
Since the anthracene derivative of the present invention exhibits
light emission of blue green to yellow green, a light-emitting
element exhibiting light emission of blue green to yellow green can
be obtained.
Here, various materials can be used as a substance in which the
anthracene derivative of the present invention is dispersed. In
addition to the substance having a high hole transporting property
and the substance having a high electron transporting property,
which are described in Embodiment Mode 2,
4,4'-bis(N-carbazolyl)-biphenyl (abbreviation: CBP),
2,2',2''-(1,3,5-benzenetriyl)-tris[1-phenyl-1H-benzimidazole]
(abbreviation: TPBI), 9,10-di(2-naphthyl)anthracene (abbreviation:
DNA), 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation:
t-BuDNA), 9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene
(abbreviation: CzPA), and the like are exemplified.
Since the anthracene derivative of the present invention has hi
luminous efficiency, a light-emitting element with high luminous
efficiency can be obtained by using the anthracene derivative of
the present invention in a light-emitting element. Also, by using
the anthracene derivative of the present invention in a
light-emitting element, a light-emitting element with a long
lifetime can be obtained.
Further, since a light-emitting element using the anthracene
derivative of the present invention is capable of green light
emission with high efficiency, the light-emitting element can be
favorably used for a full-color display. In addition, since the
light-emitting element using the anthracene derivative of the
present invention is capable of green light emission with a long
lifetime, it can be favorably used for a full-color display.
Further since the anthracene derivative of the present invention
can provide green light emission with high efficiency, white light
emission can be obtained by combining with another light emissive
material. For example, in an attempt to realize white light
emission using red (R), green (G), and blue (B) emissions which
exhibit the corresponding NTSC chromaticity coordinates, white
color cannot be obtained unless light emissions of these colors are
mixed with a proportion of approximately red (R):green (G):blue
(B)=1:6:3. That is, green light emission with high luminance is
necessary, and, therefore, the anthracene derivative of the present
invention by which green light emission with high efficiency can be
obtained is favorable for a light-emitting device.
Note that, regarding the layers other than the third layer 105, the
structure shown in Embodiment Mode 2 can be appropriately used.
Embodiment Mode 4
In this embodiment mode, a light-emitting element with a structure
different from the structures described in Embodiment Modes 2 and 3
is described.
In this embodiment mode, the third layer 105 shown in FIGS. 1A to
1C is formed by dispersing a light-emitting substance in the
anthracene derivative of the present invention, whereby light
emission from the light-emitting substance can be obtained.
In a case where the anthracene derivative of the present invention
is used as a material in which another light-emitting substance is
dispersed, a light emission color derived from the light-emitting
substance can be obtained. Further, a mixed color resulted from the
anthracene derivative of the present invention and the
light-emitting substance dispersed in the anthracene derivative can
also be obtained.
Here, various materials can be used as a light-emitting substance
dispersed in the anthracene derivative of the present invention.
Specifically, a fluorescence emitting substance that emits
fluorescence such as
4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran
(abbreviation: DCM1),
4-(dicyanomethylene)-2-methyl-6-(julolidine-4-yl-vinyl)-4H-pyran
(abbreviation: DCM2), N,N-dimethylquinacridone (abbreviation:
DMQd), or rubrene can be used. Further, a phosphorescence emitting
substance that emits phosphorescence such as
(acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III)
(abbreviation: Ir(Fdpq).sub.2(acac)),
2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinplatinum(II)
(abbreviation: PtOEP), or the like can be used.
Note that, regarding the layers other than the third layer 105, the
structure shown in Embodiment Mode 2 can be appropriately used.
Embodiment Mode 5
In this embodiment mode, a light-emitting element with a structure
different from those of Embodiment Modes 2 and 3 is described.
An anthracene derivative of the present invention has a hole
transporting property. Therefore, the layer including the
anthracene derivative of the present invention can be used between
the anode and the light-emitting layer. Specifically, the
anthracene derivative of the present invention can be used in the
first layer 103 and the second layer 104 described in Embodiment
Mode 1.
Also, in a case of applying the anthracene derivative of the
present invention as the first layer 103, it is preferable to
compose the anthracene derivative of the present invention and an
inorganic compound having an electron accepting property with
respect to the anthracene derivative of the present invention. By
using such a composite layer, carrier density of the first layer
increases, which contributes to improvement of the hole injecting
property and hole transporting property. Also, in a case of using
the composite in the first layer 103, the first layer 103 can
achieve an ohmic contact with the first electrode 102; therefore, a
material of the first electrode can be selected regardless of work
function.
As the inorganic compound used for the composite material, an oxide
of a transition metal is preferably used. Moreover, oxides of
metals belonging to Groups 4 to 8 in the periodic table can be
represented. Specifically, it is preferable to use vanadium oxide,
niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide,
tungsten oxide, manganese oxide, and rhenium oxide, because of
their high electron accepting properties. Among them, molybdenum
oxide is particularly preferable because it is stable under air,
has a low moisture absorption property, and is easily handled.
Note that this embodiment mode can be appropriately combined with
another embodiment mode.
Embodiment Mode 6
In this embodiment mode, a light-emitting element in which a
plurality of light-emitting units according to the present
invention is stacked (hereinafter, referred to as a stacked type
element) will be explained with reference to FIG. 3. This
light-emitting element is a stacked type light-emitting element
that has a plurality of light-emitting units between a first
electrode and a second electrode. A structure similar to that
described in Embodiment Modes 2 to 5 can be used for each
light-emitting unit. In other words, the light-emitting element
described in Embodiment Mode 2 is a light-emitting element having
one light-emitting unit. In this embodiment mode, a light-emitting
element having a plurality of light-emitting units will be
explained.
In FIG. 3, a first light-emitting unit 511 and a second
light-emitting unit 512 are stacked between a first electrode 501
and a second electrode 502. An electrode similar to that described
in Embodiment Mode 2 can be applied to the first electrode 501 and
the second electrode 502. The first light-emitting unit 511 and the
second light-emitting unit 512 may have the same structure or
different structures, and a structure similar to those described in
Embodiment Modes 2 to 5 can be applied.
A charge generation layer 513 includes a composite material of an
organic compound and metal oxide. The composite material of an
organic compound and metal oxide is described in Embodiment Mode 2
or 5, and includes an organic compound and metal oxide such as
vanadium oxide, molybdenum oxide, or tungsten oxide. As the organic
compound, various compounds such as an aromatic amine compound, a
carbazole derivative, a aromatic hydrocarbon, and a high molecular
weight compound (oligomer, dendrimer, polymer, or the like) can be
used. An organic compound having a hole mobility of greater than or
equal to 1.times.10.sup.-6 cm.sup.2/Vs is preferably applied as the
organic compound. However, other substances than these compounds
may also be used as long as the hole transporting properties
thereof are higher than the electron transporting properties
thereof. The composite material of an organic compound and metal
oxide is superior in carrier injecting property and carrier
transporting property, and accordingly, low-voltage driving and
low-current driving can be realized.
It is to be noted that the charge generation layer 513 may be
formed with a combination of a composite material of an organic
compound and metal oxide and other materials. For example, the
charge generation layer 513 may be formed with a combination of a
layer including the composite material of an organic compound and
metal oxide and a layer including one compound selected from
electron donating substances and a compound having a high electron
transporting property. Further, the charge generation layer 513 may
be formed with a combination of a layer including the composite
material of an organic compound and metal oxide and a transparent
conductive film.
In any case, the charge generation layer 513 is acceptable as long
as electrons are injected to one light-emitting unit and holes are
injected to the other light-emitting unit when a voltage is applied
between the first electrode 501 and the second electrode 502. For
example, in a case of applying a voltage so that a potential of the
first electrode is higher than a potential of the second electrode,
any structure is acceptable for the charge generation layer 513 as
long as the layer 513 injects electrons and holes into the first
light-emitting unit 511 and the second light-emitting unit 512,
respectively.
In this embodiment mode, the light-emitting element having two
light-emitting units is explained; however, the present invention
can be applied to a light-emitting element in which three or more
light-emitting units are stacked. By arranging a plurality of
light-emitting units between a pair of electrodes in such a manner
that the plurality of light-emitting units is partitioned with a
charge generation layer, high luminance emission can be realized at
a low current density, which contributes to enhancement of the
lifetime of the light-emitting element. In other words, a
light-emitting device capable of low-voltage driving and low-power
consuming can be realized.
This embodiment mode can be appropriately combined with another
embodiment mode.
Embodiment Mode 7
In this embodiment mode, a light-emitting device manufactured using
an anthracene derivative of the present invention will be
described.
In this embodiment mode, a light-emitting device manufactured using
the anthracene derivative of the present invention will be
explained with reference to FIGS. 4A and 4B. FIG. 4A is a top view
showing a light-emitting device, and FIG. 4B is a cross-sectional
view of FIG. 4A taken along lines A-A' and B-B'. A driver circuit
portion (source side driver circuit), a pixel portion, and a driver
circuit portion (gate side driver circuit) are denoted by reference
numerals 601, 602, and 603, respectively, and are indicated by
dotted lines. Also, a sealing substrate and a sealing material are
denoted by reference numerals 604 and 605, respectively, and a
portion surrounded by the sealing material 605 corresponds to a
space 607.
A leading wiring 608 is a wiring for transmitting a signal to be
inputted to the source side driver circuit 601 and the gate side
driver circuit 603, and this wiring 608 receives a video signal, a
clock signal, a start signal, a reset signal, and the like from an
FPC (flexible printed circuit) 609 that is an external input
terminal. It is to be noted that only the FPC is shown here;
however, the FPC may be provided with a printed wiring board (PWB).
The light-emitting device in this specification includes not only a
light-emitting device itself but also a light-emitting device
attached with an FPC or a PWB.
Subsequently, a cross-sectional structure will be explained with
reference to FIG. 4B. The driver circuit portion and the pixel
portion are formed over a substrate 610. Here, the source side
driver circuit 601, which is the driver circuit portion, and one
pixel in the pixel portion 602 are shown.
A CMOS circuit, which is a combination of an n-channel TFT 623 and
a p-channel TFT 624, is formed as the source side driver circuit
601. The driver circuit may be formed using various CMOS circuits,
PMOS circuits, or NMOS circuits. Although a driver-integration type
device, in which a driver circuit is formed over a substrate, is
described in this embodiment mode, a driver circuit is not
necessarily formed over a substrate and can be formed outside a
substrate.
The pixel portion 602 has a plurality of pixels, each of which
includes a switching TFT 611, a current control TFT 612, and a
first electrode 613 which is electrically connected to a drain of
the current control TFT 612. It is to be noted that an insulator
614 is formed so as to cover an edge portion of the first electrode
613. Here, a positive photosensitive acrylic resin film is used for
the insulator 614.
The insulator 614 is formed so as to have a curved surface having
curvature at an upper end portion or a lower end portion thereof in
order to obtain favorable coverage. For example, in a case of using
positive photosensitive acrylic resin as a material for the
insulator 614, the insulator 614 is preferably formed so as to have
a curved surface with a curvature radius (0.2 .mu.m to 3 .mu.m)
only at the upper end portion thereof. Either a negative type resin
which becomes insoluble in an etchant by photo-irradiation or a
positive type resin which becomes soluble in an etchant by
photo-irradiation can be used for the insulator 614.
A layer 616 including a light-emitting substance and a second
electrode 617 axe formed over the first electrode 613. Here, a
material having a high work function is preferably used as a
material for the first electrode 613 serving as an anode. For
example, the first electrode 613 can be formed by using stacked
layers of a titanium nitride film and a film including aluminum as
its main component; a three-layer structure of a titanium nitride
film, a film including aluminum as its main component, and a
titanium nitride film; or the like as well as a single-layer film
such as an ITO film, an indium tin oxide film including silicon, an
indium oxide film including 2 to 20 wt % of zinc oxide, a titanium
nitride film, a chromium film, a tungsten film, a Zn film, or a Pt
film. When the first electrode 613 has a stacked structure, the
electrode 613 shows low resistance enough to serve as a wiring,
giving an good ohmic contact.
In addition, the layer 616 including a light-emitting substance is
formed by various methods such as an evaporation method using an
evaporation mask, an ink-jet method, and a spin coating method. The
layer 616 including a light-emitting substance has the anthracene
derivative of the present invention described in Embodiment Mode 1.
Further, the layer 616 including a light-emitting substance may be
formed using another material including a low molecular weight
compound or a high molecular weight compound (including oligomer
and dendrimer).
As a material used for the second electrode 617, which is formed
over the layer 616 including alight-emitting substance and serves
as a cathode, a material having a low work function (Al, Mg, Li,
Ca, or an alloy or a compound thereof such as MgAg, MgIn, AlLi,
LiF, or CaF.sub.2) is preferably used. In a case where light
generated in the layer 616 including a light-emitting substance is
transmitted through the second electrode 617, stacked layers of a
metal thin film and a transparent conductive film (ITO, indium
oxide including 2 to 20 wt % of zinc oxide, indium oxide-tin oxide
including silicon or silicon oxide, zinc oxide (ZnO), or the like)
are preferably used as the second electrode 617.
By attachment of the sealing substrate 604 to the element substrate
610 with the sealing material 605, a light-emitting element 618 is
provided in the space 607 surrounded by the element substrate 610,
the sealing substrate 604, and the sealing material 605. It is to
be noted that the space 607 is filled with a an inert gas
(nitrogen, argon, or the like. There is also a case where the space
607 is filled with the sealing material 605.
It is to be noted that an epoxy-based resin is preferably used as
the sealing material 605. It is desired that the material allows as
little moisture and oxygen as possible to penetrate. As the sealing
substrate 604, a plastic substrate formed using FRP
(Fiberglass-Reinforced Plastics), PVF (polyvinyl fluoride),
polyester, acrylic resin, or the like can be used as well as a
glass substrate or a quartz substrate.
By the abovementioned processes, a light-emitting device having the
anthracene derivative of the present invention can be obtained.
Since the anthracene derivative described in Embodiment Mode 1 is
used for the light-emitting device of the present invention, a
light-emitting device having high performance can be obtained.
Specifically, a light-emitting device having a long lifetime can be
obtained.
Also, since the anthracene derivative of the present invention has
high luminous efficiency, a light-emitting device with low power
consumption can be obtained.
Further, since an anthracene derivative of the present invention is
capable of green light emission with high efficiency, the
anthracene derivative can be favorably used for a full-color
display. Further, since the anthracene derivative of the present
invention is capable of green light emission with a long lifetime,
it can be favorably used for a full-color display.
Furthermore, since the anthracene derivative of the present
invention is capable of green light emission with high efficiency,
white light emission can be obtained by combining with another
light emission material. For example, in an attempt to realize
white light emission using red (R), green (G), and blue (B)
emissions which exhibit the corresponding NTSC chromaticity
coordinates, white color cannot be obtained unless light emissions
of these colors are mixed with a proportion of approximately red
(R):green (G):blue (B)=1:6:3. That is, green light emission with
high luminance is necessary, and, therefore, the anthracene
derivative of the present invention by which green light emission
with high efficiency can be obtained is favorable for a
light-emitting device.
As described above, in this embodiment mode, an active type
light-emitting device in which driving of a light-emitting element
is controlled by a transistor is explained. Alternatively, a
passive type light-emitting device in which a light-emitting
element is driven without an element for driving such as a
transistor may also be used. FIG. 5 shows a perspective view of a
passive type light-emitting device which is manufactured by
applying the present invention. In FIG. 5, a layer 955 including a
light-emitting substance is provided between an electrode 952 and
an electrode 956 over a substrate 951. An edge of the electrode 952
is covered with an insulating layer 953. Then, a partition layer
954 is provided over the insulating layer 953. A side wall of the
partition layer 954 slopes so that a distance between one side wall
and the other side wall becomes narrow toward a substrate surface.
In other words, a cross section of the partition layer 954 in the
direction of a short side is trapezoidal, and a base (a side
expanding in a similar direction as a plane direction of the
insulating layer 953 and in contact with the insulating layer 953)
is shorter than an upper side (a side expanding in a similar
direction as the plane direction of the insulating layer 953 and
not in contact with the insulating layer 953). The partition layer
954 provided in this manner allows patterning the electrode 956. A
light-emitting device with a long lifetime can be also obtained in
the case of the passive type light-emitting device by using the
light-emitting element of the present invention. Further, a
light-emitting device with low power consumption can be
obtained.
Embodiment Mode 8
In this embodiment mode, an electronic device of the present
invention including the light-emitting device described in
Embodiment Mode 7 will be explained. The electronic device of the
present invention includes the anthracene derivative described in
Embodiment Mode 1, and has a display portion with a long lifetime.
Also, the electronic device of the present invention possesses a
display portion with reduced power consumption.
As an electronic device including a light-emitting element
fabricated using the anthracene derivative of the present
invention, a camera such as a video camera or a digital camera, a
goggle type display, a navigation system, an audio reproducing
device (car audio component stereo, audio component stereo, or the
like), a computer, a game machine, a portable information terminal
(mobile computer, mobile phone, portable game machine, electronic
book, or the like), and an image reproducing device provided with a
recording medium (specifically, a device capable of reproducing a
recording medium such as a Digital Versatile Disc (DVD) and
provided with a display device that can display the image), and the
like are given. Specific examples of these electronic devices are
shown in FIGS. 6A to 6D.
FIG. 6A shows a television device according to the present
invention, which includes a housing 9101, a supporting base 9102, a
display portion 9103, a speaker portion 9104, a video input
terminal 9105, and the like. In the television device, the display
portion 9103 has light-emitting elements similar to those described
in Embodiment Modes 2 to 5, and the light-emitting elements are
arranged in matrix. The features of the light-emitting element are
exemplified by the luminous efficiency and long lifetime. The
display portion 9103 which includes the light-emitting elements has
similar features. Therefore, in the television device, image
quality is scarcely deteriorated and low power consumption is
achieved. Therefore, deterioration compensation function circuits
and power supply circuits can be significantly reduced or downsized
in the television device, which enables reduction of the size and
weight of the housing 9101 and supporting base 9102. In the
television device according to the present invention, low power
consumption, high image quality, and small size and lightweight are
achieved; therefore, a product which is suitable for living
environment can be provided. Also, since the anthracene derivative
described in Embodiment Mode 1 is capable of green light emission,
a full-color display is possible, and a television device having a
display portion with a long life can be obtained.
FIG. 6B shows a computer according to the present invention, which
includes a main body 9201, a housing 9202, a display portion 9203,
a keyboard 9204, an external connection port 9205, a pointing
device 9206, and the like. In the computer, the display portion
9203 has light-emitting elements similar to those described in
Embodiment Modes 2 to 5, and the light-emitting elements are
arranged in matrix. The features of the light-emitting element are
given by high luminous efficiency and long lifetime. The display
portion 9203 which includes the light-emitting elements has similar
features. Therefore, in the computer, image quality is scarcely
deteriorated and lower power consumption is achieved. Due to these
features, deterioration compensation function circuits and power
supply circuits can be significantly reduced or downsized in the
computer; therefore, small sized and lightweight main body 9201 and
housing 9202 can be achieved. In the computer according to the
present invention, low power consumption, high image quality, and
small size and lightweight are achieved; therefore, a product which
is suitable for an environment can be supplied. Further, since the
anthracene derivative described in Embodiment Mode 1 is capable of
green light emission, a full-color display is possible, and a
computer having a display portion with a long lifetime can be
obtained.
FIG. 6C shows a mobile phone according to the present invention,
which includes a main body 9401, a housing 9402, a display portion
9403, an audio input portion 9404, an audio output portion 9405, an
operation key 9406, an external connection port 9407, an antenna
9408, and the like. In the mobile phone, the display portion 9403
has light-emitting elements similar to those described in
Embodiment Modes 2 to 5, and the light-emitting elements are
arranged in matrix. The features of the light-emitting element are
exemplified by high luminous efficiency and long lifetime. The
display portion 9403 which includes the light-emitting elements has
similar features. Therefore, in the mobile phone, image quality is
scarcely deteriorated and lower power consumption is achieved.
Owing to these features, deterioration compensation function
circuits and power supply circuits can be significantly reduced or
downsized in the mobile phone; therefore, small sized and
lightweight mail, body 9401 and housing 9402 can be supplied. In
the mobile phone according to the present invention, low power
consumption, high image quality, and a small size and lightweight
are achieved; therefore, a product which is suitable for carrying
can be provided. Further, since the anthracene derivative described
in Embodiment Mode 1 is capable of green light emission, a
full-color display is possible, and a mobile phone having a display
portion with a long lifetime can be obtained.
FIG. 6D shows a camera according to the present invention, which
includes a main body 9501, a display portion 9502, a housing 9503,
an external connection port 9504, a remote control receiving
portion 9505, an image receiving portion 9506, a battery 9507, an
audio input portion 9508, operation keys 9509, an eye piece portion
9510, and the like. In the camera, the display portion 9502 has
light-emitting elements similar to those described in Embodiment
Modes 2 to 5, and the light-emitting elements are arranged in
matrix. Some features of the light-emitting element are its high
luminous efficiency long lifetime. The display portion 9502 which
includes the light-emitting elements has similar features.
Therefore, in the camera, image quality is hardly deteriorated and
lower power consumption can be achieved. Such features contribute
to significant reduction and downsizing of the deterioration
compensation function circuits and power supply circuits in the
camera; therefore, a small sized and lightweight main body 9501 can
be supplied. In the camera according to the present invention, low
power consumption, high image quality, and small size and
lightweight are achieved; therefore, a product which is suitable
for carrying can be provided. Further, the anthracene derivative
described in Embodiment Mode 1 is capable of green light emission,
full-color display is possible, and a camera having a display
portion with a long lifetime can be obtained.
As described above, the applicable range of the light-emitting
device of the present invention is so wide that the light-emitting
device can be applied to electronic devices in various fields. By
using the anthracene derivative of the present invention,
electronic devices which have display portions with a long lifetime
can be provided.
The light-emitting device of the present invention can also be used
as a lighting device. One mode using the light-emitting element of
the present invention as the lighting device will be explained with
reference to FIG. 7.
FIG. 7 shows an example of a liquid crystal display device using
the light-emitting device of the present invention as a backlight.
The liquid crystal display device shown in FIG. 7 includes a
housing 901, a liquid crystal layer 902, a backlight 903, and a
housing 904, and the liquid crystal layer 902 is connected to a
driver IC 905. The light-emitting device of the present invention
is used for the backlight 903, and current is supplied through a
terminal 906.
By using the light-emitting device of the present invention as the
backlight of the liquid crystal display device, a backlight with
reduced power consumption and high luminous efficiency can be
obtained. The light-emitting device of the present invention is a
lighting device with plane light emission, and can have a large
area. Therefore, the backlight can have a large area, and a liquid
crystal display device having a large area can be obtained.
Furthermore, the light-emitting device of the present invention has
a thin shape and has low power consumption; therefore, a thin shape
and low power consumption of a display device can also be achieved.
Since the light-emitting device of the present invention has a long
lifetime, a liquid crystal display device using the light-emitting
device of the present invention also has a long lifetime.
FIG. 8 shows an example of the light-emitting device to which the
present invention is applied. In this Figure, an example for the
application to a table lamp as a lighting device is illustrated. A
table lamp shown in FIG. 8 has a housing 2001 and a light source
2002, and the light-emitting device of the present invention is
used as the light source 2002. The light-emitting device of the
present invention has high luminous efficiency and has a long
lifetime; therefore, a table lamp also has high luminous efficiency
and a long lifetime.
FIG. 9 shows an example of a light-emitting device to which the
present invention is applied. This Figure demonstrates an example
for the application to an indoor lighting device 3001. Since the
light-emitting device of the present invention can also have a
large area, the light-emitting device of the present invention can
be used as a lighting device having a large emission area. Further,
the light-emitting device of the present invention has a thin shape
and consumes low power; therefore, the light-emitting device of the
present invention can be used as a lighting device having a thin
shape and low-power consumption. A television device 3002 according
to the present invention as explained in FIG. 6A is placed in a
room in which the light-emitting device fabricated by the present
invention is used as the indoor lighting device 3001, and public
broadcasting and movies can be watched. In such a case, since both
of the devices consume low power, a powerful image can be watched
in a bright room without concern about electricity charges.
Embodiment 1
In this embodiment, a synthetic method of
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (101), will be
specifically described.
##STR00109##
[Step 1] Synthesis of 2-bromo-9,10-diphenylanthracene
(i) Synthesis of 2-bromo-9,10-anthraquinone
A synthetic scheme of 2-bromo-9,10-anthraquinone is shown in
(C-1).
##STR00110##
46 g (206 mmol) of copper bromide (II) and 500 mL of acetonitrile
were put into a 1 L three-neck flask, and was added 17.3 g (168
mmol) of tert-butyl nitrite into the suspension, which was followed
by heating at 65.degree. C. Thereafter, 25 g (111.0 mmol) of
2-amino-9,10-anthraquinone was added into the mixture, and then the
mixture was stirred for 6 hours at the same temperature. After the
reaction, the reaction mixture was poured into 3M-hydrochloric acid
and stirred for 3 hours. Then the precipitate was filtered and
washed with water and then with ethanol. The precipitate was
dissolved in toluene, and the resulting solution was filtered
through Florisil, celite, and then alumina. The filtrate was
concentrated, and the residue was recrystallized with chloroform
and hexane, giving 18.6 g of 2-bromo-9,10-anthraquinone as a
cream-colored solid in 58% yield.
(ii) Synthesis of
2-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol
A synthetic scheme of
2-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol is shown in
(C-2).
##STR00111##
4.90 g (16.95 mmol) of 2-bromo-9,10-anthraquinone was put into a
300 three-neck flask, and the atmosphere of the flask was
substituted with nitrogen. Into the flask was added 100 mL of
tetrahydrofuran (THF), and 17.76 mL (37.29 mmol) of a dibutyl
ether-solution of phenyllithium was dropwised, which was followed
by stirring for about 12 hours at room temperature. After the
reaction, the solution was washed with water, and the aqueous layer
was extracted with ethyl acetate. The organic layer was dried over
magnesium sulfate, filtered and concentrated to give
2-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol as the
target compound.
(iii) Synthesis of 2-bromo-9,10-diphenylanthracene
A synthetic scheme of 2-bromo-9,10-diphenylanthracene is shown in
(C-3).
##STR00112##
7.55 g (16.95 mmol) of the obtained
2-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 5.06 g
(30.51 mmol) of potassium iodide, 9.70 g (91.52 mmol) of sodium
phosphinate monohydrate, and 50 mL of glacial acetic acid were put
into a 500 mL three-neck flask, and the mixture was heated at
120.degree. C. for 2 hours. Thereafter, 30 mL of 50% phosphinic
acid was added to the mixture, and the mixture was stirred for 1
hour at 120.degree. C. After the reaction, the mixture was washed
with water, and the aqueous layer was extracted with ethyl acetate.
The organic layer was dried over magnesium sulfate, filtered, and
concentrated. The residue was dissolved in toluene, and the
solution was filtered through celite, Florisil, and then alumina.
The filtrate was concentrated, and the residue was recrystallized
with chloroform and hexane, giving 5.1 g of
2-bromo-9,10-diphenylanthracene as a light yellow solid in 74%
yield.
[Step 2] Synthetic Method of 2DPAPA
A synthetic scheme of 2DPAPA is shown in (C-4).
##STR00113##
1.8 g (4.40 mmol) of 2-bromo-9,10-diphenylanthracene synthesized in
Step 1 of Embodiment 1, 1.78 g (5.28 mmol) of
N,N,N'-triphenyl-1,4-phenylenediamine (DPA), 0.126 g (0.220 mmol)
of bis(dibenzylideneacetone)palladium (0), and 2.11 g (21.99 mmol)
of sodium tert-butoxide were put into a 100 mL three-neck flask,
and the atmosphere in the flask was substituted with nitrogen.
Further, 30 mL of toluene and 0.44 g (0.220 mmol) of
tri(tert-butyl)phosphine (a 10% hexane solution) were added to the
flask, and the solution was heated at 80.degree. C. for 6 hours.
After the reaction, the solution was washed with water, and the
aqueous layer was extracted with ethyl acetate. The organic layer
was dried over magnesium sulfate, filtered and concentrated, and
the residue was dissolved in toluene, which was followed by
filtration through celite, Florisil, and then alumina. The filtrate
was concentrated, and then the residue was recrystallized with
chloroform, methanol, and hexane, resulting in 2.24 g of the target
compound as a yellow solid in 77% yield. By a nuclear magnetic
resonance measurement (NMR), it was confirmed that this compound
was
9,10-diphenyl-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthracene
(abbreviation: 2DPAPA).
.sup.1H NMR data of 2DPAPA is shown below. .sup.1H NMR
(DMSO-d.sub.6, 300 MHz): .delta.=6.90-7.14 (m, 15H), 7.25-7.37 (m,
10H), 7.44-7.52 (m, 8H), 7.57-7.66 (m, 3H). The .sup.1H NMR chart
is shown in FIGS. 11A and 11B. Note that the range of 6.5 ppm to
8.0 ppm in FIG. 11A is expanded and shown in FIG. 11B.
The decomposition temperature (T.sub.d) of 2DPAPA, measured with a
thermogravimetric/differential thermal analyzer (type TG/DTA 320,
manufactured by Seiko Instruments Inc.), was found to be
395.9.degree. C., meaning high thermal stability of this
compound.
The absorption spectrum of a toluene solution of 2DPAPA is shown in
FIG. 12. In addition, an absorption spectrum of a thin film of
2DPAPA is shown in FIG. 13. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2DPAPA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 12 and 13, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 12 and 13, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 442 nm, and in the case of the
thin film, absorption was observed at around 452 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
430 nm) of 2DPAPA is shown in FIG. 14, and an emission spectrum of
the thin film (excitation wavelength, of 452 nm) of 2DPAPA is shown
in FIG. 15. In each of FIGS. 14 and 15, a horizontal axis shows
wavelength (nm) and a vertical axis shows emission intensity (an
arbitrary unit). In the case of the toluene solution, the maximum
emission wavelength was 539 nm (excitation wavelength of 430 nm),
and in the case of the thin film, the maximum emission wavelength
was 543 nm (excitation wavelength of 452 nm).
The HOMO level of 2DPAPA in a thin film state which was measured by
a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.28 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 13, the optical energy gap was estimated to be 2.46 eV,
which means that LUMO level of 2DPAPA is -2.82 eV.
Embodiment 2
In this embodiment, a synthetic method of
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (201), is
specifically described.
##STR00114##
[Step: 1] Synthesis of N-phenyl-(9-phenyl-9H-carbozole-3-yl)amine
(abbreviation: PCA)
(i) Synthesis of 3-bromo-9-phenylcarbazole
A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in
(C-5).
##STR00115##
24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer
flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g
(100 mmol) of N-bromosuccinimide was slowly added, and the solution
was stirred for about 12 hours at room temperature. This solution
was dropped into 1 L of ice water while stiffing. A white solid
precipitated was collected by suction filtration, and then washed
with water three times. This solid was dissolved in 150 mL of
diethyl ether, and the solution was washed with a saturated aqueous
solution of sodium bicarbonate and then with water. The organic
layer was dried over magnesium sulfate, filtered, and concentrated,
and then the residue was dissolved in ca. 50 mL of ethanol. The
precipitate formed as a white solid was collected by suction
filtration and dried, giving 28.4 g (88% yield) of
3-bromo-9-phenylcarbazole as white powder.
(ii) Synthesis of N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine
(abbreviation: PCA)
A synthetic scheme of N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine
(abbreviation: PCA) is shown in (C-6).
##STR00116##
Into a 500 mL three-neck flask were added 19 g (60 mmol) of
3-bromo-9-phenylcarbazole, 340 mg (0.6 mmol) of
bis(dibenzylideneacetone)palladium (0), 1.6 g (3.0 mmol) of
1,1-bis(diphenylphosphino)ferrocene, and 13 g (180 mmol) of sodium
tert-butoxide, and the atmosphere in the flask was substituted with
nitrogen. Thereafter, 110 mL of dehydrated xylene and 7.0 g (75
mmol) of aniline were added to the mixture. This mixture was heated
and stirred for 7.5 hours at 90.degree. C. After the reaction was
completed, about 500 mL of hot toluene was added to the solution,
and this solution was filtered through Florisil, alumina, and
celite. The obtained filtrate was concentrated, and hexane and
ethyl acetate were added to the residue, which was followed by
irradiation with ultrasound. A solid precipitated was collected by
suction filtration and dried to give 15 g (75% yield) of
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA) as
cream colored powder. By a nuclear magnetic resonance measurement
(NMR), it was confirmed that this compound was
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=6.84 (t, J=6.9 Hz, 1H), 6.97 (d, J=7.8
Hz, 2H), 7.20-7.61 (m, 13H), 7.90 (s, 1H), 8.04 (d, J=7.8 Hz, 1H).
The .sup.1H NMR chart is shown in FIGS. 16A and 16B. Note that the
range of 5.0 ppm to 9.0 ppm in FIG. 16A is expanded and shown in
FIG. 16B.
[Step 2] Synthetic Method of 2PCAPA
A synthetic scheme of 2PCAPA is shown in (C-7).
##STR00117##
1.8 g (4.40 mmol) of 2-bromo-9,10-diphenylanthracene synthesized in
Step 1 of Embodiment 1, 1.76 g (5.28 mmol) of
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA),
0.126 g (0.220 mmol) of bis(dibenzylideneacetone)palladium (0), and
2.11 g (21.99 mmol) of sodium tert-butoxide were put into a 100 mL
three-neck flask, and the atmosphere in the flask was substituted
with nitrogen. 30 mL of toluene and 0.44 g (0.220 mmol) of
tri(tert-butyl)phosphine (10% hexane solution) were added to the
flask, and the mixture was heated at 80.degree. C. with stirring
for 6 hours. After the reaction, the solution was washed with
water, and the aqueous layer was extracted with ethyl acetate. The
organic layer was dried over magnesium sulfate. After filtration
and concentration of the organic layer, the residue was dissolved
in toluene, and the solution was filtered through celite, Florisil,
and then alumina. The filtrate was concentrated, and the residue
was recrystallized with chloroform, methanol, and hexane, obtaining
2.33 g of the target compound as a yellow solid in 80% yield. By
the nuclear magnetic resonance analysis (NMR), it was confirmed
that this compound was
9,10-diphenyl-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anthracene
(abbreviation: 2PCAPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR
(CDCl.sub.3, 300 MHz): .delta.=6.92-6.97 (m, 1H), 7.11-7.32 (m,
16H), 7.39-7.66 (m, 15H), 7.88-7.97 (m, 2H). Also, the .sup.1H NMR
chart is shown in FIGS. 17A and 17B. Note that the range of 6.5 ppm
to 8.0 ppm in FIG. 17A is expanded and shown in FIG. 17B.
The decomposition temperature (T.sub.d) of 2PCAPA, measured with a
thermogravimetric/differential thermal analyzer (type TG/DTA 320,
manufactured by Seiko Instruments Inc.), was found to be
410.1.degree. C., meaning high thermal stability of this
compound.
The absorption spectrum of a toluene solution of 2PCAPA is shown in
FIG. 18. In addition, an absorption spectrum of a thin film of
2PCAPA is shown in FIG. 19. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2PCAPA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 18 and 19, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 18 and 19, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 442 nm, and in the case of the
thin film, absorption was observed at around 448 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
430 nm) of 2PCAPA is shown in FIG. 20, and an emission spectrum of
the thin film (excitation wavelength of 448 nm) of 2PCAPA is shown
in FIG. 21. In each of FIGS. 20 and 21, a horizontal axis shows
wavelength (nm) and a vertical axis shows emission intensity (an
arbitrary unit). In the case of the toluene solution, the maximum
light emission wavelength was 508 nm (excitation wavelength of 430
nm), and in the case of the thin film, the maximum emission
wavelength was 537 nm (excitation wavelength of 448 nm).
The HOMO level of 2PCAPA in a thin film state which was measured by
a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.26 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 19, the optical energy gap was estimated to be 2.47 eV,
which means that LUMO level of 2PCAPA is -2.79 eV.
An oxidation-reduction characteristic of 2PCAPA was explored by a
cyclic voltammetry (CV) measurement. For the measurement, an
electrochemical analyzer (ALS model 600A, manufactured by BAS Inc.)
was used.
As for a solution used in the CV measurement, dehydrated
N,N-dimethylformamide (DMF) (manufactured by Aldrich, 99.8%,
catalog number: 22705-6) was used as a solvent.
Tetra-n-butylammonium perchlorate (n-Bu.sub.4NClO.sub.4)
(manufactured by Tokyo Chemical Industry Co., Ltd., catalog number:
T0836), a supporting electrolyte, was dissolved in DMF at the
concentration of 100 mmol/L to prepare the electrolysis solution.
The sample solution was prepared by dissolving the sample in the
electrolysis solution at a concentration of 1 mmol/L. A platinum
electrode (a PIE platinum electrode, manufactured by BAS Inc.) was
used as a working electrode. A platinum electrode (a VC-3 Pt
counter electrode (5 cm), manufactured by BAS Inc.) was used as a
counter electrode. An Ag/Ag.sup.+ electrode (an RE5 non-aqueous
solvent type reference electrode, manufactured by BAS Inc.) was
used as a reference electrode. The measurement was conducted at
room temperature.
An oxidation characteristic of 2PCAPA was evaluated in the
following manner. The potential of the working electrode with
respect to a reference electrode was swept from -0.23 V to 0.60 V,
which was followed by sweeping the potential from 0.60 V to -0.23
V. This cycle was set as one cycle, and 100 cycles were performed.
Also, a reduction characteristic of 2PCAPA was evaluated in the
following manner. The potential of the working electrode with
respect to the reference electrode was swept from -0.41 V to -2.50
V, which was followed by sweeping the potential from -2.50 V to
-0.41 V. This cycle was set as one cycle, and 100 cycles were
performed. Sweeping speed of the CV measurement was set to be 0.1
V/s.
The CV measurement result of an oxidation side of 2PCAPA and the CV
measurement result of a reduction side of 2PCAPA are shown in FIGS.
22 and 23, respectively. In each of FIGS. 22 and 23, a horizontal
axis shows a potential (V) of the working electrode with respect to
the reference electrode, and a vertical axis shows a current value
(.mu.A) that flowed between the working electrode and the counter
electrode. From FIG. 22, a current exhibiting oxidation was
observed around -0.47 V (vs. Ag/Ag.sup.+). From FIG. 23, a current
exhibiting reduction was observed around -2.22 V (vs.
Ag/Ag.sup.+).
In spite of the fact that 100 cycles of sweeping were repeated, a
peak position and a peak intensity at the CV curve scarcely changed
in the oxidation and reduction, which reveals that the anthracene
derivative of the present invention is extremely stable against
repetition of the oxidation and reduction.
Embodiment 3
In this embodiment, a synthetic method of
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anthrace-
ne (abbreviation: 2DPABPhA), which is the anthracene derivative of
the present invention represented by Structural Formula (115), is
specifically described.
##STR00118##
[Step 1] Synthesis of 9,10-di(2-biphenylyl)-2-bromoanthracene
A synthetic scheme of 9,10-di(2-biphenylyl)-2-bromoanthracene is
shown in (C-8) to (C-10).
##STR00119##
##STR00120##
##STR00121##
22.84 g (98.00 mmol) of 2-bromobiphenyl was put into a 500 mL
three-neck flask, and the atmosphere of the flask was substituted
with nitrogen. Into the flask was added 100 mL of tetrahydrofuran
(THF), followed by dropwising 68.66 mL (107.80 mmol) of
n-butyllithium (1.57 mol/L hexane solution) at -78.degree. C. After
stirring for 5 hours, 160 mL of THF containing 8.5 g (29.40 mmol)
of 2-bromo-9,10-anthraquinone was dropwised to this solution under
nitrogen, and the solution was stirred for about 12 hours while the
reaction temperature was allowed to gradually increase to room
temperature. After the reaction, into the solution was added water,
and the precipitate formed was filtered, giving
9,10-di(2-biphenylyl)-2-bromo-9,10-dihydroanthracene-9,10-diol as a
cream colored solid.
18.32 g (30.66 mmol) of the obtained
9,10-di(2-biphenylyl)-2-bromo-9,10-dihydroanthracene-9,10-diol,
9.16 g (55.19 mmol) of potassium iodide, 17.55 g (165.56 mmol) of
sodium phosphinate monohydrate, and 150 mL of glacial acetic acid
were put into a three-neck flask, and the mixture was stirred for 5
hours at 120.degree. C. Thereafter, 100 mL of 50% phosphinic acid
was added to the mixture, followed by stirring for 1 hour at
120.degree. C. After the reaction, the solution was washed with
water, and the precipitate was filtered, recrystallized with
chloroform and hexane, obtaining 11.4 g of
9,10-di(2-biphenylyl)-2-bromoanthracene as a light yellow solid in
66% yield.
[Step 2] Synthetic Method of 2DPABPhA
A synthetic scheme of 2DPABPhA is shown in (C-11).
##STR00122##
2.0 g (3.56 mmol) of 9,10-di(2-biphenylyl)-2-bromoanthracene
synthesized in Step 1 of Embodiment 3, 1.44 g (4.27 mmol) of
N,N,N'-triphenyl-1,4-phenylenediamine (DPA), 0.102 g (0.178 mmol)
of bis(dibenzylideneacetone)palladium (0), and 1.71 g (17.81 mmol)
of sodium tert-butoxide were put into a 100 mL three-neck flask,
and the atmosphere in the flask was substituted with nitrogen. 30
mL of toluene and 0.36 g (0.178 mmol) of tri(tert-butyl)phosphine
(10% hexane solution) were added to the flask, and the solution was
heated at 80.degree. C. with stirring for 7 hours. After the
reaction, the solution was washed with water, and the aqueous layer
was extracted with ethyl acetate. The organic layer was dried over
magnesium sulfate, filtered and concentrated, and the residue was
dissolved in toluene. This toluene solution was filtered through
celite, Florisil, and then alumina. The filtrate was concentrated,
and the residue was recrystallized with chloroform and methanol,
giving 2.5 g of the target compound as a yellow solid in 87% yield.
By the nuclear magnetic resonance measurement (NMR), it was
confirmed that this compound was
9,10-di(2-biphenylyl)-2-[N-(4-diphenylaminophenyl)-N-phenylamino]anth-
racene (abbreviation: 2DPABPhA).
The .sup.1H NMR data of this compound is shown below. .sup.1H-NMR
(CDCl.sub.3, 300 MHz): .delta.=6.78-7.08 (m, 24H), 7.12-7.30 (m,
10H), 7.32-7.59 (m, 10H). The .sup.1H NMR chart is shown in each of
FIGS. 24A and 24B. Note that the range of 6.5 ppm to 8.0 ppm in
FIG. 24A is expanded and shown in FIG. 24B.
The decomposition temperature (T.sub.d) of 2DPABPhA, measured with
a thermogravimetric/differential thermal analyzer (type TG/DTA 320,
manufactured by Seiko Instruments Inc.), was found to be
419.8.degree. C., meaning high thermal stability of this
compound.
The absorption spectrum of a toluene solution of 2DPABPhA is shown
in FIG. 25. In addition, an absorption spectrum of a thin film of
2DPABPhA is shown in FIG. 26. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2DPABPhA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 25 and 26, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 25 and 26, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 446 nm, and in the case of the
thin film, absorption was observed at around 449 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
430 nm) of 2DPABPhA is shown in FIG. 27, and an emission spectrum
of the thin film (excitation wavelength of 430 nm) of 2DPABPhA is
shown in FIG. 28. In each of FIGS. 27 and 28, a horizontal axis
shows wavelength (nm) and a vertical axis shows emission intensity
(an arbitrary unit). In the case of the toluene solution, the
maximum emission wavelength was 542 nm (excitation wavelength of
430 nm), and in the case of the thin film, the maximum emission
wavelength was 548 nm (excitation wavelength of 449 nm).
The HOMO level of 2DPABPhA in a thin film state which was measured
by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.28 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 26, the optical energy gap was estimated to be 2.47 eV,
which means that LUMO level of 2DPABPhA is -2.81 eV.
Embodiment 4
In this embodiment, a synthetic method of
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA), which is the anthracene derivative
of the present invention represented by Structural Formula (215),
is specifically described.
##STR00123##
[Step 1] Synthetic Method of 2PCABPhA
A synthetic scheme of 2PCABPhA is shown in (C-12).
##STR00124##
2.8 g (5.0 mmol) of 9,10-di(2-biphenylyl)-2-bromoanthracene
synthesized in Step 1 of Embodiment 3, 1.67 g (5.0 mmol) of
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA)
synthesized in Step 1 of Embodiment 2, 0.14 g (0.25 mmol) of
bis(dibenzylideneacetone)palladium, and 2.4 g (25 mmol) of sodium
tert-butoxide were put into a 100 mL three-neck flask, and the
atmosphere in the flask was substituted with nitrogen. 20 mL of
toluene and 1.5 g (0.75 mmol) of tri(tert-butyl)phosphine (10%
hexane solution) were added to the flask, and the solution was
stirred for 6 hours at 80.degree. C. After the reaction, the
solution was washed with water, and the aqueous layer was extracted
with ethyl acetate. The organic layer was dried over magnesium
sulfate, filtered, and concentrated, and the residue was dissolved
in toluene. The solution was filtered through celite, Florisil, and
then alumina. The filtrate was concentrated, and the residue was
recrystallized with toluene and hexane, obtaining 3.4 g of a
target, compound as a yellow solid in 83% yield. By a nuclear
magnetic resonance measurement (NMR), it was confirmed that this
compound was
9,10-di(2-biphenylyl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-yl)amino]anth-
racene (abbreviation: 2PCABPhA).
.sup.1H NMR data of this compound is shown below. .sup.1H-NMR
(CDCl.sub.3, 300 MHz): .delta.=6.74-7.09 (m, 16H), 7.14-7.29 (m,
8H), 7.32-7.62 (m, 16H), 7.75-7.97 (m, 2H). The .sup.1H NMR chart
is shown in each of FIGS. 29A and 29B. Note that the range of 6.5
ppm to 8.5 ppm in FIG. 29A is expanded and shown in FIG. 29B.
The decomposition temperature (T.sub.d) of 2PCABPhA, measured with
a thermogravimetric/differential thermal analyzer (type TG/DTA 320,
manufactured by Seiko Instruments Inc.), was found to be
423.7.degree. C., meaning high thermal stability of this
compound.
The absorption spectrum of a toluene solution of 2PCABPhA is shown
in FIG. 30. In addition, an absorption spectrum of a thin film of
2PCABPhA is shown in FIG. 31. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2PCABPhA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 30 and 31, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 30 and 31, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 440 nm, and in the case of the
thin film, absorption was observed at around 449 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
430 nm) of 2PCABPhA is shown in FIG. 32, and an emission spectrum
of the thin film (excitation wavelength of 449 nm) of 2PCABPhA is
shown in FIG. 33. In each of FIGS. 32 and 33, a horizontal axis
shows wavelength (nm) and a vertical axis shows emission intensity
(an arbitrary unit). In the case of the toluene solution, the
maximum emission wavelength was 509 nm (excitation wavelength of
430 nm), and in the case of the thin film, the maximum emission
wavelength was 534 nm (excitation wavelength of 449 nm).
The HOMO level of 2PCABPhA in a thin film state which was measured
by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.29 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 31, the optical energy gap was estimated to be 2.46 eV,
which means that LUMO level of 2DPAPA is -2.83 eV.
An oxidation-reduction characteristic of 2PCABPhA was explored by a
cyclic voltammetry (CV) measurement. For the measurement, an
electrochemical analyzer (ALS model 600A, manufactured by BAS Inc.)
was used.
As for a solution used in the CV measurement, dehydrated
N,N-dimethylformamide (DMF) (manufactured by Aldrich, 99.8%,
catalog number: 22705-6) was used as a solvent.
Tetra-n-butylammonium perchlorate (n-Bu.sub.4NClO.sub.4)
(manufactured by Tokyo Chemical Industry Co., Ltd., catalog number:
T0836), a supporting electrolyte, was dissolved in DMF at the
concentration of 100 mmol/L to prepare the electrolysis solution.
The sample solution was prepared by dissolving the sample in the
electrolysis solution at a concentration of 1 mmol/L. A platinum
electrode (a PIE platinum electrode, manufactured by BAS Inc.) was
used as a working electrode. A platinum electrode (a VC-3 Pt
counter electrode (5 cm), manufactured by BAS Inc.) was used as a
counter electrode. An Ag/Ag.sup.+ electrode (an RE5 non-aqueous
solvent type reference electrode, manufactured by BAS Inc.) was
used as a reference electrode. The measurement was conducted at
room temperature.
An oxidation characteristic of 2PCABPhA was evaluated in the
following manner. The potential of the working electrode with
respect to a reference electrode was swept from -0.23 V to 0.70 V,
which was followed by sweeping the potential from 0.70 V to -0.23
V. This cycle was set as one cycle, and 100 cycles were performed.
Also, a reduction characteristic of 2PCABPhA was evaluated in the
following manner. The potential of the working electrode with
respect to the reference electrode was swept from -0.36 V to -2.50
V, which was followed by sweeping the potential from -2.50 V to
-0.36 V. This cycle was set as one cycle, and 100 cycles were
performed. Sweeping speed of the CV measurement was set to be 0.1
V/s.
The CV measurement result of an oxidation side of 2PCABPhA and the
CV measurement result of a reduction side of 2PCABPhA are shown in
FIGS. 34 and 35, respectively. In each of FIGS. 34 and 35, a
horizontal axis shows a potential (V) of the working electrode with
respect to the reference electrode, and a vertical axis shows a
current value (.mu.A) that flowed between the working electrode and
the counter electrode. From FIG. 34, the current exhibiting
oxidation was observed around 0.49 V (vs. Ag/Ag.sup.+ electrode).
From FIG. 35, the current exhibiting reduction was observed around
-2.20 V (vs. Ag/Ag.sup.+ electrode).
In spite of the fact that 100 cycles of sweeping were repeated, a
peak position and a peak intensity at the CV curve scarcely changed
in the oxidation and reduction, which reveals that the anthracene
derivative of the present invention is extremely stable against
repetition of the oxidation and reduction.
Embodiment 5
In this embodiment, a synthetic method of
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA), which is the anthracene
derivative of the present invention represented by Structural
Formula (315), is specifically described.
##STR00125##
[Step 1] Synthesis of 4-(carbazol-9-yl)diphenylamine (abbreviation:
YGA)
(i) Synthesis of N-(4-bromophenyl)carbazole
A synthetic scheme of N-(4-bromophenyl)carbazole is shown in
(C-13).
##STR00126##
56.3 g (0.24 mol) of 1,4-dibromobenzene, 31.3 g (0.18 mol) of
carbazole, 4.6 g (0.024 mol) of copper iodide, 66.3 g (0.48 mol) of
potassium carbonate, and 2.1 g (0.008 mol) of 18-crown-6-ether were
put into a 300 mL three-neck flask, and the atmosphere of the flask
was substituted with nitrogen. Thereafter, 8 mL of
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation:
DMPU) was added, and then the mixture was stirred for 6 hours at
180.degree. C. After the reaction mixture was cooled to room
temperature, the precipitate was removed by suction filtration. The
filtrate was washed with a diluted hydrochloric acid, a saturated
sodium bicarbonate aqueous solution, and then brine, and dried with
magnesium sulfate. After drying, the mixture was filtered, and the
filtrate was concentrated to yield an oil which was purified by
silica gel column chromatography (hexane:ethyl acetate=9:1). The
resulting solid was recrystallized with chloroform and hexane,
obtaining 20.7 g of N-(4-bromophenyl)carbazole as a light brown
plate-like crystal in 35% yield. By the nuclear magnetic resonance
measurement (NMR), it was confirmed that this compound was
N-(4-bromophenyl)carbazole.
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=8.14 (d, J=7.8 Hz, 2H), 7.73 (d, J=8.7
Hz, 2H), 7.46 (d, J=8.4 Hz, 2H), 7.42-7.26 (m, 6H).
(ii) Synthesis of 4-(carbazol-9-yl)diphenylamine (abbreviation:
YGA)
A synthetic scheme of 4-(carbazol-9-yl)diphenylamine (abbreviation:
YGA) is shown in (C-14).
##STR00127##
5.4 g (17.0 mmol) of N-(4-bromophenyl)carbazole obtained in the
abovementioned step (i), 1.8 mL (20.0 mmol) of aniline, 100 mg
(0.17 mmol) of bis(dibenzylideneacetone)palladium (0), and 3.9 g
(40 mmol) of sodium tert-butoxide were put into a 200 mL three-neck
flask, and the atmosphere of the flask was substituted with
nitrogen. Thereafter, 0.1 mL of tri(tert-butyl)phosphine (10 wt %
hexane solution) and 50 mL of toluene were added to the flask, and
the solution was stirred for 6 hours at 80.degree. C. The reaction
mixture was filtered through Florisil, celite, and then alumina.
The filtrate was washed with water, and then brine, and dried with
magnesium sulfate. The mixture was filtered, and the filtrate was
concentrated to give an oily substance which was purified by silica
gel column chromatography (hexane:ethyl acetate=9:1), providing 4.1
g of 4-(carbazol-9-yl)diphenylamine (abbreviation: YGA) in 73%
yield. It was continued by a nuclear magnetic resonance measurement
(NMR) that this compound was 4-(carbazol-9-yl)diphenylamine
(abbreviation: YGA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, DMSO-d.sub.6): .delta.=8.47 (s, 1H), 8.22 (d, J=7.8 Hz, 2H),
7.44-7.16 (m, 14H), 6.92-6.87 (m, 1H). FIGS. 36A and 36B each show
a .sup.1H NMR chart. Note that the range of 6.5 ppm to 8.5 ppm in
FIG. 36A is expanded and shown in FIG. 36B.
[Step 2] Synthetic Method of 2YGABPhA
A synthetic scheme of 2YGABPhA is shown in (C-15).
##STR00128##
2.0 g (3.5 mmol) of 9,10-di(2-biphenylyl)-2-bromoanthracene
synthesized in Step 1 of Embodiment 3, 597 mg (3.5 mmol) of
4-(carbazol-9-yl)diphenylamine (abbreviation: YGA) synthesized in
Step 1 of Embodiment 5, and 2.0 g (21 mmol) of sodium tert-butoxide
were put into a 100 mL three-neck flask, and the atmosphere of the
flask was substituted with nitrogen. Thereafter, 30 mL of toluene
and 0.1 mL of tri(tert-butyl)phosphine (10% hexane solution) were
added to the flask, and the solution was degassed under reduced
pressure. After degassing, 20 mg (0.035 mmol) of
bis(dibenzylideneacetone)palladium (0) was added to the solution,
and the solution was stirred for 3 hours at 80.degree. C. After the
reaction, the reaction solution was washed with water and brine in
this order, and then the organic layer was dried with magnesium
sulfate. After filtration, the filtrate was concentrated, and the
obtained solid was purified by silica gel column chromatography
(hexane:toluene=6:4). The resulting solid was recrystallized with
dichloromethane-hexane, obtaining 2.0 g of the target compound as a
yellow solid in 69% yield. It was confirmed by a nuclear magnetic
resonance measurement (NMR) that this compound was
9,10-di(2-biphenylyl)-2-{N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylamino}ant-
hracene (abbreviation: 2YGABPhA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=6.86-7.08 (m, 14H), 7.13 (d, J=9.0 Hz,
2H), 7.21-7.24 (m, 3H), 7.26-7.64 (m, 19H), 8.15 (d, J=7.8 Hz, 2H).
The .sup.1H NMR chart is shown in each of FIGS. 37A and 37B. Note
that the range of 6.5 ppm to 8.0 ppm in FIG. 37A is expanded and
shown in FIG. 37B.
The absorption spectrum of a toluene solution of 2YGABPhA is shown
in FIG. 38. In addition, an absorption spectrum of a thin film of
2YGABPhA is shown in FIG. 39. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2YGABPhA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 38 and 39, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 38 and 39, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 430 nm, and in the case of the
thin film, absorption was observed at around 435 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
370 nm) of 2YGABPhA is shown in FIG. 40, and an emission spectrum
of the thin film (excitation wavelength of 435 nm) of 2YGABPhA is
shown in FIG. 41. In each of FIGS. 40 and 41, a horizontal axis
shows wavelength (nm) and a vertical axis shows emission intensity
(an arbitrary unit). In the case of the toluene solution, the
maximum emission wavelength was 491 nm (excitation wavelength of
370 nm), and in the case of the thin film, the maximum emission
wavelength was 495 nm (excitation wavelength of 435 nm).
The HOMO level of 2YGABPhA in a thin film state which was measured
by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.36 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 39, the optical energy gap was estimated to be 2.56 eV,
which means that LUMO level of 2YGABPhA is -2.80 eV.
Embodiment 6
In this embodiment, a light-emitting element of the present
invention is described with reference to FIG. 10. The chemical
formulae of the materials used in this embodiment are shown
below.
##STR00129##
The element structure of the light-emitting element manufactured in
this embodiment is summarized in Table 1. In Table 1, the mixture
ratios are all represented in weight ratios.
TABLE-US-00001 TABLE 1 The structure of the light-emitting elements
1-10 Layer including Hole Electron Electron First composite
transporting Emission transporting injection Second No. electrode
material* layer layer layer layer electrode 1 ITSO NPB:MoOx NPB
CzPA:2DPAPA Alq LiF Al 110 nm (4:1) 10 nm (1:0.2) 30 nm 1 nm 200 nm
50 nm 40 nm 2 CzPA:2DPAPA BPhen (1:0.2) 30 nm 40 nm 3 CzPA:2PCAPA
Alq (1:0.1) 30 nm 40 nm 4 CzPA:2PCAPA BPhen (1:0.1) 30 nm 40 nm 5
CzPA:2DPABPhA Alq (1:0.5) 30 nm 40 nm 6 CzPA:2DPABPhA BPhen (1:0.5)
30 nm 40 nm 7 CzPA:2PCABPhA Alq (1:0.5) 30 nm 40 nm 8 CzPA:2PCABPhA
BPhen (1:0.5) 30 nm 40 nm 9 CzPA:2YGABPhA Alq 40 nm 30 nm 10
CzPA:2YGABPhA BPhen 40 nm 30 nm *The ratios shown in parentheses
are weight ratios.
A fabrication method of the light-emitting element of this
embodiment is described below.
First, a film of indium tin oxide containing silicon oxide (ITSO)
was formed by sputtering over a glass substrate 2101 to form a
first electrode 2102. Note that the film thickness of the first
electrode was 110 nm, and an area of the electrode was 2 mm.times.2
mm.
Next, the substrate over which the first electrode was formed was
fixed to a substrate holder provided in a vacuum evaporation
apparatus, so that a surface over which the first electrode was
formed faced down. Then, after reducing the pressure of the vacuum
evaporation apparatus to about 10.sup.-4 Pa, a layer 2103
containing a composite material, which was formed of an organic
compound and an inorganic compound, was formed over the first
electrode 2102 by co-evaporating
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
and molybdenum oxide (VI). The film thickness of the layer 2103 was
to be 50 nm, and the ratio of NPB and molybdenum oxide (VI) was
adjusted to be 4:1 (=NPB:molybdenm oxide) in weight ratio. Note
that the co-evaporation method is an evaporation method in which
evaporation is carried out from a plurality of evaporation sources
at the same time in one treatment chamber.
Subsequently, a film of
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
was formed at a thickness of 10 nm over the layer 2103 containing
the composite material by the evaporation method using the
resistance heating system, thereby forming a hole transporting
layer 2104.
Further, by co-evaporating
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA)
and an anthracene derivative of the present invention, a
light-emitting layer 2105 with a thickness of 40 nm was formed over
the hole transporting layer 2104. The weight ratio of CzPA and the
anthracene derivative for each light-emitting element was adjusted
to be the value shown in Table 1.
Thereafter, tris(8-quinolinolato)aluminum (abbreviation: Alq) was
formed at a film thickness of 30 nm over the light-emitting layer
2105 in the cases of light-emitting elements 1, 3, 5, 7, and 9 by
means of the evaporation method using the resistance heating
system, resulting in the fabrication of an electron transporting
layer 2106. In the cases of light-emitting elements 2, 4, 6, 8, and
10, a film of bathophenanthroline (abbreviation: BPhen) was formed
with a thickness of 30 nm to form the electron transporting layer
2106.
Furthermore, a film of lithium fluoride (LiF) was formed at a
thickness of 1 nm over the electron transporting layer 2106 to form
an electron injecting layer 2107.
Finally, by forming a film of aluminum with a film thickness of 200
nm over the electron injecting layer 2107 by means of the
evaporation method using the resistance heating system, a second
electrode 2108 was formed. Accordingly, light-emitting elements 1
to 10 were fabricated.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 1 are shown in FIGS. 42, 43, and 44,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 45. Further, FIGS. 46 and 47
demonstrate time dependence of normalized luminance and time
dependence of operation voltage, respectively, of the
light-emitting element 1 when initial luminance was 3000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 1 at luminance of 3000 cd/m.sup.2 was (x=0.36, y=0.60), and
light emission was yellow green. Current efficiency at luminance of
3000 cd/m.sup.2 was 17.4 cd/A, meaning that high current efficiency
was exhibited. In addition, as shown in FIG. 45, maximum emission
wavelength at a current of 1 mA was 540 nm. It can be concluded
from FIG. 46 that the light-emitting element 1 has a long lifetime,
since 84% of the initial luminance was maintained even after 600
hours.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 2 are shown in FIGS. 48, 49, and 50,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 51. A CIE chromaticity
coordinate of the light-emitting element 2 at luminance of 3000
cd/m.sup.2 was (x=0.33, y=0.63), and light emission was green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 19.3 cd/A,
meaning that high current efficiency was exhibited. Power
efficiency at luminance of 3000 cd/m.sup.2 was 17.8 lm/W,
indicating that the element 2 can be operated at low power
consumption. In addition, as shown in FIG. 51, maximum emission
wavelength at a current of 1 mA was 535 nm.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 3 are shown in FIGS. 52, 53, and 54,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 55. Further, FIGS. 56 and 57
demonstrate time dependence of normalized luminance and time
dependence of operation voltage, respectively, of the
light-emitting element 3 when initial luminance was 3000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 3 at luminance of 3000 cd/m.sup.2 was (x=0.31, y=0.63), and
light emission was green. Current efficiency at luminance of 3000
cd/m.sup.2 was 14.5 cd/A, meaning that high current efficiency was
exhibited. In addition, as shown in FIG. 55, maximum emission
wavelength at a current of 1 mA was 521 nm. It can be concluded
from FIG. 56 that the light-emitting element 3 has a long lifetime,
since 87% of the initial luminance was maintained even after 300
hours.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 4 are shown in FIGS. 58, 59, and 60,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 61. A CIE chromaticity
coordinate of the light-emitting element 4 at luminance of 3000
cd/m.sup.2 was (x=0.30, y=0.62), and light emission was green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 16.3 cd/A,
meaning that high current efficiency was exhibited. The power
efficiency at luminance of 3000 cd/m.sup.2 was 16.4 lm/W,
indicating that the element 4 can be operated at low power
consumption. In addition, as shown in FIG. 61, maximum emission
wavelength at a current of 1 mA was 520 nm.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 5 are shown in FIGS. 62, 63, and 64,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 65. Further, FIGS. 66 and 67
demonstrate time dependence of normalized luminance and time
dependence of operation voltage, respectively, of the
light-emitting element 5 when initial luminance was 3000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 5 at luminance of 3000 cd/m.sup.2 was (x=0.39, y=0.59), and
light emission was yellow green. Current efficiency at luminance of
3000 cd/m.sup.2 was 16.3 cd/A, meaning that high current efficiency
was exhibited. In addition, as shown in FIG. 65, maximum, emission
wavelength at a current of 1 mA was 546 nm. It can be concluded
from FIG. 66 that the light-emitting element 5 has a long lifetime,
since 74% of the initial luminance was maintained even after 1600
hours.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 6 are shown in FIGS. 68, 69, and 70,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 71. A CIE chromaticity
coordinate of the light-emitting element 6 at luminance of 3000
cd/m.sup.2 was (x=0.37, y=0.60), and light emission was yellow
green. Current efficiency at luminance of 3000 cd/m.sup.2 was 17.6
cd/A, meaning that high current efficiency was exhibited. The power
efficiency at luminance of 3000 cd/m.sup.2 was 18:6 lm/W,
indicating that the element 6 can be operated at low power
consumption. In addition, as shown in FIG. 71, maximum emission
wavelength at a current of 1 mA was 545 nm.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 7 are shown in FIGS. 72, 73, and 74,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 75. Further, FIGS. 76 and 77
demonstrate time dependence of normalized luminance and time
dependence of operation voltage, respectively, of the
light-emitting element 7 when initial luminance was 3000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 7 at luminance of 3000 cd/m.sup.2 was (x=0.31, y=0.63), and
light emission was green. Current efficiency at luminance of 3000
cd/m.sup.2 was 13.0 cd/A, meaning that high current efficiency was
exhibited. In addition, as shown in FIG. 75, maximum emission
wavelength at a current of 1 mA was 520 nm. It can be concluded
from FIG. 76 that the light-emitting element 7 has a long lifetime,
since 69% of the initial luminance was maintained even after 1300
hours.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 8 are shown in FIGS. 78, 79, and 80,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 81. A CIE chromaticity
coordinate of the light-emitting element 8 at luminance of 3000
cd/m.sup.2 was (x=0.31, y=0.63), and light emission was green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 15.74 cd/A,
meaning that high current efficiency was exhibited. The power
efficiency at luminance of 3000 cd/m.sup.2 was 14.9 lm/W,
indicating that the element 8 can be operated at low power
consumption. In addition, as shown in FIG. 81, maximum emission
wavelength at a current of 1 mA was 522 nm.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 9 are shown in FIGS. 82, 83, and 84,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 85. A CIE chromaticity
coordinate of the light-emitting element 9 at luminance of 3000
cd/m.sup.2 was (x=0.21, y=0.49), and light emission was blue green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 8.9 cd/A,
meaning that high current efficiency was exhibited. In addition, as
shown in FIG. 85, maximum emission wavelength at a current of 1 mA
was 491 nm.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 10 are shown in FIGS. 86, 87, and 88,
respectively. Also, the emission spectrum which was obtained at a
current of 1 mA is illustrated in FIG. 89. A CIE chromaticity
coordinate of the light-emitting element 10 at luminance of 3000
cd/m.sup.2 was (x=0.21, y=0.49), and light emission was blue green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 12.1 cd/A,
meaning that high current efficiency was exhibited. The power
efficiency at luminance of 3000 cd/m.sup.2 was 11.6 lm/W,
indicating that the element 10 can be operated at low power
consumption. In addition, as shown in FIG. 89, maximum emission
wavelength at a current of 1 mA was 492 nm.
Embodiment 7
In this embodiment, a synthetic method of
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA), which is the anthracene derivative of the
present invention represented by Structural Formula (219), is
specifically described.
##STR00130##
[Step 1] Synthesis of N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine
(abbreviation: PCN)
A synthetic scheme of N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine
(abbreviation: PCN) is shown in (C-16).
##STR00131##
3.7 g (10 mmol) of 3-iodine-9-phenylcarbazole, 1.6 g (5 mmol) of
1-aminonaphthalene, 60 mg (0.1 mmol) of
bis(dibenzylideneacetone)palladium (0), 0.2 mL (0.5 mmol) of
tri(tert-butyl)phosphine (10 wt % hexane solution), and 3.0 g (30
mmol) of sodium tert-butoxide were put into a 100 mL three-neck
flask, and after nitrogen substitution was carried out in the
flask, 12 mL of dehydrated xylene was added to the mixture. The
reaction mixture was stirred for 7 hours at 90.degree. C. under
nitrogen. After the reaction was completed, about 200 mL of hot
toluene was added to the reaction mixture, and the mixture was
filtered through Florisil, alumina, and celite. The obtained
filtrate was concentrated, and this concentrated solution was
purified by silica gel column chromatography (eluting solvent was
toluene:hexane=1:1). Recrystallization of the obtained solid with a
mixed solvent of ethyl acetate and hexane gave 1.5 g of
N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine as light brown powder
in 79% yield. It was confirmed by a nuclear magnetic resonance
measurement (NMR) that this compound was
N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine (abbreviation:
PCN).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, DMSO-d.sub.6): .delta.=7.13-7.71 (m, 15H), 7.85-7.88 (m, 1H),
8.03 (s, 1H), 8.15 (d, J=7.8 Hz, 1H), 8.24 (s, 1H), 8.36-8.39 (m,
1H).
[Step 2] Synthesis of 2PCNPA
A synthetic scheme of 2PCNPA is shown in (C-17).
##STR00132##
3.5 g (8.6 mmol) of 2-bromo-9,10-diphenylanthracene synthesized in
Step 1 of Embodiment 1, 3.2 g (9.4 mmol) of
N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine (abbreviation: PCN),
0.25 g (0.43 mmol) of bis(benzylideneacetone)palladium (0), and 2.1
g (21 mmol) of sodium tert-butoxide were put in a 200 mL three-neck
flask, and the atmosphere of the flask was substituted with
nitrogen. Thereafter, 50 mL of toluene and 0.86 g (0.43 mmol) of
tri(tert-butyl)phosphine (10% hexane solution) were added to the
mixture, and this reaction mixture was stirred for 5 hours at
80.degree. C. After the reaction was completed, the reaction
solution was washed with water, and the aqueous layer was extracted
with ethyl acetate. The extracted solution was combined with the
organic layer, and then dried with magnesium sulfate. After drying,
this mixture was subjected to suction filtration, and the filtrate
was concentrated. The obtained residue was purified by silica gel
column chromatography (eluent: toluene). The obtained solid was
recrystallized with a mixed solvent of chloroform and hexane,
giving 2.6 g of
2[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracene
(abbreviation: 2PCNPA) as yellow powder in 42% yield. It was
confirmed by a nuclear magnetic resonance measurement (NMR) that
this compound was
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR
(CDCl.sub.3, 300 MHz): .delta.=6.67-6.68 (m, 1H), 7.02-7.38 (m,
15H), 7.44-7.70 (m, 16H), 7.88-8.01 (m, 4H). The .sup.1H NMR chart
is shown in each of FIGS. 90A and 90B. Note that the range of 6.5
ppm to 8.5 ppm in FIG. 90A was expanded and shown in FIG. 90B.
Thermogravimetric/differential thermal analysis (TG-DTA) of 2PCNPA
was carried out. In measuring, a high vacuum differential type
differential thermal balance (type DTA2410SA, manufactured by
Bruker AXS K.K.) was used. When measuring was carried out under
reduced pressure of 10 Pa, it was found that the 5% weight-loss
temperature was 289.degree. C., which is indicative of high thermal
stability of 2PCNPA.
The absorption spectrum of a toluene solution of 2PCNPA is shown in
FIG. 91. In addition, an absorption spectrum of a thin film of
2PCNPA is shown in FIG. 92. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2PCNPA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 91 and 92, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 91 and 92, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 438 nm, and in the case of the
thin film, absorption was observed at around 442 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
430 nm) of 2PCNPA is shown in FIG. 93, and an emission spectrum of
the thin film (excitation wavelength of 442 nm) of 2PCNPA is shown
in FIG. 94. In each of FIGS. 93 and 94, a horizontal axis shows
wavelength (nm) and a vertical axis shows emission intensity (an
arbitrary unit). In the case of the toluene solution, the maximum
emission wavelength was 503 nm (excitation wavelength of 445 nm),
and in the case of the thin film, the maximum emission wavelength
was 522 nm (excitation wavelength of 430 nm).
The HOMO level of 2PCNPA in a thin film state which was measured by
a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.21 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 92, the optical energy gap was estimated to be 2.48 eV,
which means that LUMO level of 2PCNPA is -2.73 eV.
An oxidation-reduction characteristic of 2PCNPA was explored by a
cyclic voltammetry (CV) measurement. For the measurement, an
electrochemical analyzer (ALS model 600A, manufactured by BAS Inc.)
was used.
As for a solution used in the CV measurement, dehydrated
N,N-dimethylformamide (DMF) (manufactured by Aldrich, 99.8%,
catalog number: 22705-6) was used as a solvent.
Tetra-n-butylammonium perchlorate (n-Bu.sub.4NClO.sub.4)
(manufactured by Tokyo Chemical Industry Co., Ltd., catalog number:
T0836), a supporting electrolyte, was dissolved in DMF at the
concentration of 100 mmol/L to prepare the electrolysis solution.
The sample solution was prepared by dissolving the sample in the
electrolysis solution at a concentration of 1 mmol/L. A platinum
electrode (a PTE platinum electrode, manufactured by BAS Inc.) was
used as a working electrode. A platinum electrode (a VC-3 Pt
counter electrode (5 cm), manufactured by BAS Inc.) was used as a
counter electrode. An Ag/Ag.sup.+ electrode (an RE5 non-aqueous
solvent type reference electrode, manufactured by BAS Inc.) was
used as a reference electrode. The measurement was conducted at
room temperature.
An oxidation characteristic of 2PCNPA was evaluated in the
following manner. The potential of the working electrode with
respect to a reference electrode was swept from -0.40 V to 0.60 V,
which was followed by sweeping the potential from 0.60 V to -0.40
V. This cycle was set as one cycle, and 100 cycles were performed.
Also, a reduction characteristic of 2PCNPA was evaluated in the
following manner. The potential of the working electrode with
respect to the reference electrode was swept from -0.15 V to -2.55
V, which was followed by sweeping the potential from -2.55 V to
-0.15 V. This cycle was set as one cycle, and 100 cycles were
performed. Sweeping speed of the CV measurement was set to be 0.1
V/s.
The results of the CV measurement of the oxidation side and
reduction side of 2PCNPA are shown in FIGS. 95 and 96,
respectively. In each of FIGS. 95 and 96, a horizontal axis shows a
voltage (V) of the working electrode with respect to the reference
electrode, and a vertical axis shows a current value (.mu.A) that
flowed between the working electrode and the counter electrode.
From FIG. 95, a current exhibiting oxidation was observed around
0.41 V (vs. Ag/Ag.sup.+). Also, from FIG. 96, a current exhibiting
reduction was observed around -2.33 V (vs. Ag/Ag.sup.+).
In spite of the fact that 100 cycles of sweeping were repeated, a
peak position and a peak intensity at the CV curve scarcely changed
in the oxidation and reduction, which reveals that the anthracene
derivative of the present invention is extremely stable against
repetition of the oxidation and reduction.
Embodiment 8
In this embodiment, a synthetic method of
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA), which is the anthracene derivative
of the present invention represented by Structural Formula (220),
is specifically described.
##STR00133##
[Step 1] Synthesis of N,9-di(1-naphthyl)-9H-carbazole-3-amine
(abbreviation: NCN)
(i) Synthesis of 9-(1-naphthyl)carbazole
A synthetic scheme of 9-(1-naphthyl)carbazole is shown in
(C-18).
##STR00134##
21 g (0.1 mol) of 1-bromonaphthalene, 17 g (0.1 mol) of carbazole,
950 mg (5 mmol) of copper iodide (I), 33 g (240 mmol) of potassium
carbonate, and 660 mg (2.5 mmol) of 18-crown-6-ether were put into
a 500 mL three-neck flask, and nitrogen substitution was carried
out in the flask. To this mixture was added 80 mL of
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation:
DMPU), which was followed by stirring for 6 hours at 170.degree. C.
under nitrogen. To this reaction mixture was further added 10 g (50
mmol) of 1-bromonaphthalene, 2.0 g (10 mmol) of copper iodide (I),
and 2.6 g (10 mmol) of 18-crown-6-ether, and stirring was further
conducted for 7.5 hours at 170.degree. C. Furthermore, to this
reaction mixture was added 10 g (50 mmol) of 1-bromonaphthalene,
and additional stirring was carried out for 6 hours at 180.degree.
C. After the reaction was completed, to this reaction mixture was
added about 200 mL of toluene and about 100 mL of 1 mol/L
hydrochloric acid, and then the mixture was filtered through
celite. The obtained filtrate was filtered through Florisil and
celite. The obtained filtrate was separated into an organic layer
and an aqueous layer, and after this organic layer was washed with
1 mol/L hydrochloric acid and then with water, the organic layer
was dried over magnesium sulfate. This suspension was filtered
through Florisil and celite. The filtrate was concentrated to give
an oily substrate, and methanol was added to this oily substrate,
followed by irradiation with ultrasound to precipitate a solid. The
solid precipitated was collected by suction filtration, giving 22 g
of 9-(1-naphthyl)carbazole as white powder (75% yield). The Rf
values (SiO.sub.2, eluent; hexane:ethyl acetate=10:1) of
9-(1-naphthyl)carbazole, 1-bromonaphthalene, and carbazole were
0.61, 0.74, and 0.24, respectively.
(ii) Synthesis of 3-bromo-9-(1-naphthyl)carbazole
A synthetic scheme of 3-bromo-9-(1-naphthyl)carbazole is shown in
(C-19).
##STR00135##
5.9 g (20 mmol) of 9-(1-naphthyl)carbazole was put into a 500 mL
Meyer flask, and 50 mL of ethyl acetate and 50 mL of toluene were
added thereto, and the reaction mixture was stirred. Then, 3.6 g
(20 mmol) of N-bromosuccinimide was slowly added to the solution,
and the solution was stirred for about 170 hours (one week) at room
temperature. After this solution was washed with water, the organic
layer was dried with magnesium sulfate. Filtration and
concentration of the reaction mixture gave 7.4 g of
3-bromo-9-(1-naphthyl)carbazole as white powder (99% yield). The Rf
values (SiO.sub.2, eluent; hexane:ethyl acetate=2:1) of
3-bromo-9-(1-naphthyl)carbazole and 9-(1-naphthyl)carbazole were
0.43 and 0.35, respectively.
(iii) Synthesis of N,9-di(1-naphthyl)-9H-carbazole-3-amine
(abbreviation: NCN)
A synthetic scheme of N,9-di(1-naphthyl)-9H-carbazole-3-amine
(abbreviation NCN) is shown in (C-20).
##STR00136##
3.7 g (10 mmol) of 3-bromo-9-(1-naphthyl)carbazole, 1.7 g (12 mmol)
of 1-naphthylamine, 58 mg (0.1 mmol) of
bis(dibenzylideneacetone)palladium (0), 600 .mu.L (0.3 mmol) of
tri(tert-butyl)phosphine (10% hexane solution), and 1.5 g (15 mmol)
of sodium tert-butoxide were put into a 100 mL three-neck flask,
and nitrogen substitution was carried out in a flask. Thereafter,
20 mL of dehydrated xylene was added to this mixture. Then, this
reaction mixture was heated and stirred for 7 hours at 110.degree.
C. under nitrogen. After the reaction was completed, about 400 mL
of toluene was added to this reaction mixture, and the mixture was
filtered through Florisil, alumina and then celite. After the
obtained filtrate was washed with water, the organic layer was
dried with magnesium sulfate. This suspension was filtered through
Florisil, alumina, and then celite, and the obtained filtrate was
concentrated. The resulting solid was purified by silica gel column
chromatography (toluene:hexane=1:1) to give 2.2 g of light brown
powder (51% yield). It was confirmed by a nuclear magnetic
resonance measurement (NMR) that this light brown powder was
N,9-di(1-naphthyl)-9H-carbazole-3-amine (abbreviation: NCN). Rf
values (SiO.sub.2, eluent; hexane:ethyl acetate=5:1) of
N,9-di(1-naphthyl)-9H-carbazole-3-amine,
3-bromo-9-(1-naphthyl)carbazole, and 1-naphthylamine were 0.46,
0.68, and 0.22, respectively.
[Step 2] Synthesis of 2NCNPA
A synthetic scheme of 2NCNPA is shown in (C-21).
##STR00137##
2.1 g (5.0 mmol) of 2-bromo-9,10-diphenylanthracene, 2.2 g (5.1
mmol) of NCN, 29 g (50 .mu.mol) of
bis(dibenzylideneacetone)palladium (0), 300 .mu.L (0.2 mmol) of
tri(tert-butyl)phosphine (10% hexane solution), and 1.0 g (10 mmol)
of sodium tert-butoxide were put into a 100 mL three-neck flask,
and nitrogen substitution was carried out in the flask. Thereafter,
20 mL of dehydrated xylene was added to this mixture. Then, this
reaction mixture was heated and stirred for 4 hours at 110.degree.
C. under nitrogen. After the reaction was completed, about 300 mL
of toluene was added to this reaction mixture, and this mixture was
filtered through Florisil, alumina, and then celite. After the
obtained filtrate was washed with water, the organic layer was
dried with magnesium sulfate. This suspension was filtered through
Florisil, alumina, and then celite, and the resulting filtrate was
concentrated. The obtained solid was purified by silica gel column
chromatography (toluene:hexane=1:1). To the oily residue obtained
was added hexane, and the mixture was then irradiated with
ultrasound to precipitate a solid. This solid was collected by
suction filtration, giving 1.1 g of the target compound as
yellow-green powder (29% yield). It was confirmed by a nuclear
magnetic resonance measurement (NMR) that this yellow-green powder
was
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=6.73 (d, J=2.4 Hz, 1H), 6.84 (d, =8.7 Hz,
1H), 6.96 (d, J=8.1 Hz, 1H), 7.04-7.70 (m, 29H), 7.89 (d, J=7.8 Hz,
1H), 7.99-8.06 (m, 5H). The .sup.1H NMR chart is shown in each of
FIGS. 97A and 97B. Note that the range of 6.5 ppm to 8.5 ppm in
FIG. 97A is expanded and shown in FIG. 97B.
The absorption spectrum of a toluene solution of 2NCNPA is shown in
FIG. 98. In addition, an absorption spectrum of a thin film of
2NCNPA is shown in FIG. 99. An ultraviolet-visible
spectrophotometer (type V550, manufactured by Japan Spectroscopy
Corporation) was used for measurement. The spectrum of the solution
was measured in a quartz cell. The sample of the thin film was
fabricated by vapor deposition of 2NCNPA over a quartz substrate.
The absorption spectra of the solution and the thin film are shown
in FIGS. 98 and 99, respectively, which were obtained by
subtracting the spectrum of the quartz substrate from the
corresponding raw spectra. In each of FIGS. 98 and 99, a horizontal
axis shows wavelength (nm) and a vertical axis shows absorption
intensity (an arbitrary unit). In the case of the toluene solution,
absorption was observed at around 448 nm, and in the case of the
thin film, absorption was observed at around 465 nm. Further, an
emission spectrum of the toluene solution (excitation wavelength of
300 nm) of 2NCNPA is shown in FIG. 100, and an emission spectrum of
the thin film (excitation wavelength of 446 nm) of 2NCNPA is shown
in FIG. 101. In each of FIGS. 100 and 101, a horizontal axis shows
wavelength (nm) and a vertical axis shows emission intensity (an
arbitrary unit). In the case of the toluene solution, the maximum
emission wavelength was 505 nm (excitation wavelength of 300 nm),
and in the case of the thin film, the maximum emission wavelength
was 529 nm (excitation wavelength of 446 nm).
The HOMO level of 2NCNPA in a thin film state which was measured by
a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air was -5.26 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film shown
in FIG. 99, the optical energy gap was estimated to be 2.47 eV,
which means that LUMO level of 2NCNPA is -2.79 eV.
Thermogravimetric/differential thermal analysis (TG-DTA) of 2NCNPA
was carried out. In measuring, a high vacuum differential type
differential thermal balance (type DTA2410SA, manufactured by
Broker AXS K.K.) was used. When measuring was carried out under
reduced pressure of 10 Pa, it was found that the 5% weight-loss
temperature was 400.degree. C., which is indicative of high thermal
stability of 2NCNPA.
Further, a glass transition temperature was measured using a
differential scanning calorimeter (DSC, manufactured by
PerkinElmer, Inc., Pyris 1). First, a sample was heated to
300.degree. C. at 40.degree. C./min to melt the sample, and then
cooled to room temperature at 10.degree. C./min. Thereafter, the
temperature was raised to 300.degree. C. at 10.degree. C./min. As a
result, it was found that the glass transition temperature
(T.sub.g) of 2NCNPA was 174.degree. C., which means that 2NCNPA has
a high glass transition temperature.
An oxidation-reduction characteristic of 2NCNPA was explored by a
cyclic voltammetry (CV) measurement. For the measurement, an
electrochemical analyzer (ALS model 600A, manufactured by BAS Inc.)
was used.
As for a solution used in the CV measurement, dehydrated
N,N-dimethylformamide (DMF) (manufactured by Aldrich, 99.8%,
catalog number: 22705-6) was used as a solvent.
Tetra-n-butylammonium perchlorate (n-Bu.sub.4NClO.sub.4)
(manufactured by Tokyo Chemical Industry Co., Ltd., catalog number:
T0836), a supporting electrolyte, was dissolved in DMF at the
concentration of 100 mmol/L to prepare the electrolysis solution.
The sample solution was prepared by dissolving the sample in the
electrolysis solution at a concentration of 1 mmol/L. A platinum
electrode (a PIE platinum electrode, manufactured by BAS Inc.) was
used as a working electrode. A platinum electrode (a VC-3 Pt
counter electrode (5 cm), manufactured by BAS Inc.) was used as a
counter electrode. An Ag/Ag.sup.+ electrode (an RE5 non-aqueous
solvent type reference electrode, manufactured by BAS Inc.) was
used as a reference electrode. The measurement was conducted at
room temperature.
An oxidation characteristic of 2NCNPA was evaluated in the
following manner. The potential of the working electrode with
respect to a reference electrode was swept from -0.07 V to 0.55 V,
which was followed by sweeping the potential from 0.55 V to -0.07
V. This cycle was set as one cycle, and 100 cycles were performed.
Also, a reduction characteristic of 2NCNPA was evaluated in the
following manner. The potential of the working electrode with
respect to the reference electrode was swept from -0.32 V to -2.45
V, which was followed by sweeping the potential from -2.45 V to
-0.32 V. This cycle was set as one cycle, and 100 cycles were
performed. Sweeping speed of the CV measurement was set to be 0.1
V/s.
The CV measurement result of the oxidation and reduction sides of
2NCNPA are shown in FIGS. 110 and 111, respectively. In each of
FIGS. 110 and 111, a horizontal axis shows a voltage (V) of the
working electrode with respect to the reference electrode, and a
vertical axis shows a current value (.mu.A) that flowed between the
working electrode and the counter electrode. From FIG. 110, the
current exhibiting oxidation was observed around 0.39 V (vs.
Ag/Ag.sup.+). Also, from FIG. 111, a current exhibiting reduction
was observed around -2.32 V (vs. Ag/Ag.sup.+).
In spite of the fact that 100 cycles of sweeping were repeated, a
peak position and a peak intensity at the CV curve scarcely changed
in the oxidation and reduction, which reveals that the anthracene
derivative of the present invention is extremely stable against
repetition of the oxidation and reduction.
Embodiment 9
In this embodiment, a light-emitting element of the present
invention is described with reference to FIG. 10.
A manufacturing method of a light-emitting element of this
embodiment is shown below.
First, a film of indium tin oxide containing silicon oxide (ITSO)
was formed by sputtering over the glass substrate 2101 to form the
first electrode 2102. Note that the film thickness of the first
electrode 2102 was 110 nm, and the area of the electrode was 2
mm.times.2 mm.
Next, the substrate over which the first electrode was formed was
fixed to a substrate holder provided in a vacuum evaporation
apparatus, so that a surface over which the first electrode was
formed faced down. Then, after reducing pressure of the vacuum
evaporation apparatus to about 10.sup.-4 Pa, the layer 2103
containing a composite material, which contains an organic compound
and an inorganic compound, was formed over the first electrode 2102
by co-evaporating 4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl
(abbreviation: NPB) and molybdenum oxide (VI). The film thickness
was to be 50 nm, and a ratio of NPB and molybdenum oxide (VI) was
adjusted to be 4:1 (=NPB:molybdenum oxide) in weight ratio.
Subsequently, a film of
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
was formed over the layer 2103 containing a composite material to
have a thickness of 10 nm by the evaporation method using
resistance heating system, thereby forming the hole transporting
layer 2104.
Further, by co-evaporating
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA)
and
2-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)-amino]-9,10-diphenylanthracen-
e (abbreviation: 2PCNPA), which is an anthracene derivative of the
present invention represented by Structural Formula (219), the
light-emitting layer 2105 with a thickness of 40 nm was formed over
the hole transporting layer 2104. Here, a rate of evaporation was
adjusted so that the weight ratio of CzPA and 2PCNPA was 1:0.05
(=CzPA:2PCNPA).
Thereafter, the electron transporting layer 2106 was formed over
the light-emitting layer 2105 by forming a film of
bathophenanthroline (abbreviation: BPhen) to have a film thickness
of 30 nm by means of the evaporation using resistance heating
system.
Further, the electron injecting layer 2107 was formed over the
electron transporting layer 2106 by fowling a film of lithium
fluoride with a thickness of 1 nm.
Finally, by forming a film of aluminum as the second electrode 2108
with a film thickness of 200 nm over the electron injecting layer
2107 using the evaporation method by resistance heating system, a
light-emitting element 11 was fabricated.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 11 are shown in FIGS. 102, 103, and
104, respectively. Also, the emission spectrum which was obtained
at a current of 1 mA is illustrated in FIG. 105. A CIE chromaticity
coordinate of the light-emitting element 11 at luminance of 3270
cd/m.sup.2 was (x=0.27, y=0.62), and light emission was green.
Current efficiency at luminance of 3270 cd/m.sup.2 was 16.1 cd/A,
meaning that high current efficiency was exhibited. In addition, as
shown in FIG. 105, maximum emission wavelength at a current of 1 mA
was 518 nm.
Embodiment 10
In this embodiment, a light-emitting element of the present
invention is described with reference to FIG. 10.
A fabrication method of a light-emitting element of this embodiment
is shown below.
First, a film of indium tin oxide containing silicon oxide (ITSO)
was formed by sputtering over the glass substrate 2101 to form the
first electrode 2102. Note that the film thickness of the first
electrode 2102 was 110 nm, and the area of the electrode was 2
mm.times.2 mm.
Next, the substrate over which the first electrode was formed was
fixed to a substrate holder provided in a vacuum evaporation
apparatus, so that a surface over which the first electrode was
formed faced down. Then, after reducing pressure of the vacuum
evaporation apparatus to about 10.sup.-4 Pa, the layer 2103
containing a composite material, which contains an organic compound
and an inorganic compound, was formed over the first electrode 2102
by co-evaporating 4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl
(abbreviation: NPB) and molybdenum oxide (VI). The film thickness
was to be 50 nm, and a ratio of NPB and molybdenum oxide (VI) was
adjusted to be 4:1 (=NPB:molybdenum oxide) in weight ratio.
Subsequently, a film of
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
was formed over the layer 2103 containing a composite material to
have a thickness of 10 inn by the evaporation method using
resistance heating system, thereby forming the hole transporting
layer 2104.
Further, by co-evaporating
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA)
and
2-{N-(1-naphthyl)-N-[9-(1-naphthyl)carbazol-3-yl]amino}-9,10-diphenylanth-
racene (abbreviation: 2NCNPA), which is an anthracene derivative of
the present invention represented by Structural Formula (220), the
light-emitting layer 2105 with a thickness of 40 nm was formed over
the hole transporting layer 2104. Here, a rate of evaporation was
adjusted so that the weight ratio of CzPA and 2NCNPA was 1:0.01
(=CzPA:2NCNPA).
Thereafter, the electron transporting layer 2106 was formed over
the light-emitting layer 2105 by forming a film of
bathophenanthroline (abbreviation: BPhen) to have a film thickness
of 30 nm by means of the evaporation using resistance heating
system.
Further, the electron injecting layer 2107 was formed over the
electron transporting layer 2106 by forming a film of lithium
fluoride with a thickness of 1 nm.
Finally, by forming a film of aluminum as the second electrode 2108
with a film thickness of 200 nm over the electron injecting layer
2107 using the evaporation method by resistance heating system, a
light-emitting element 12 was fabricated.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 12 are shown in FIGS. 106, 107, and
108, respectively. Also, the emission spectrum which was obtained
at a current of 1 mA is illustrated in FIG. 109. A CIE chromaticity
coordinate of the light-emitting element 12 at luminance of 3090
cd/m.sup.2 was (x=0.28, y=0.62), and light emission was green.
Current efficiency at luminance of 3090 cd/m.sup.2 was 14.0 cd/A,
meaning that high current efficiency was exhibited. In addition, as
shown in FIG. 109, maximum emission wavelength at a current of 1 mA
was 511 nm.
Embodiment 11
In this embodiment, a synthetic method of
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (301), is
specifically described.
##STR00138##
[Step 1] Synthetic Method of 2YGAPA
A synthetic method of 2YGAPA is shown in (C-22).
##STR00139##
2.0 g (4.1 mmol) of 2-bromo-9,10-diphenylanthracene synthesized in
Step 1 of Embodiment 1, 1.0 g (10 mmol) of sodium tert-butoxide,
1.4 g (4.1 mmol) of 4-(carbazol-9-yl)diphenylamine and 0.1 g (0.2
mmol) of bis(dibenzylideneacetone)palladium (0) were put into a 100
mL three-neck flask, and the inside of the flask was substituted
with nitrogen. 30 mL of toluene and 0.1 mL of 10 wt % hexane
solution of tri(tert-butyl)phosphine were added to this mixture.
Then, this mixture was heated and stirred for 5 hours at 80.degree.
C. After the reaction, toluene was added to a reaction mixture, and
this suspension was washed with a saturated sodium carbonate
aqueous solution and then with brine. The aqueous layer and organic
layer were separated, and the organic layer was subjected to
suction filtration through Florisil, celite, and alumina, and the
filtrate was obtained. The obtained filtrate was concentrated to
give a solid. The obtained solid was recrystallized with a mixed
solvent of chloroform and hexane, which provided 2.2 g of the
target compound as a yellow solid in 81% yield. By the nuclear
magnetic resonance measurement (NMR), it was confirmed that this
compound was
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA).
.sup.1H NMR data of 2YGAPA is shown below. .sup.1H NMR (300 MHz,
CDCl.sub.3): .delta.=7.05-7.12 (m, 1H), 7.13-7.74 (m, 31H), 8.16
(d, J=6.8 Hz, 2H). The .sup.1H NMR chart is shown in each of FIGS.
112A and 112B. Note that the range of 6.5 ppm to 8.5 ppm in FIG.
112A is expanded and shown in FIG. 112B.
The absorption spectrum of a toluene solution of 2YGAPA is shown in
FIG. 113. An ultraviolet-visible spectrophotometer (type V550,
manufactured by Japan Spectroscopy Corporation) was used for
measurement. The absorption spectrum of the solution is shown in
FIG. 113, which was obtained by subtracting the spectrum of the
quartz substrate from the raw spectra of the sample solution
charged in a quartz cell. In FIG. 113, a horizontal axis shows
wavelength (nm) and a vertical axis shows absorption intensity (an
arbitrary unit). In the case of the toluene solution, absorption
was observed at around 428 nm. Further, an emission spectrum of the
toluene solution (excitation wavelength of 430 nm) of 2YGAPA is
shown in FIG. 114. In FIG. 114, a horizontal axis shows wavelength
(nm) and a vertical axis shows emission intensity (an arbitrary
unit). In the case of the toluene solution, the maximum emission
wavelength was 486 nm (excitation wavelength of 430 nm).
The HOMO level of 2YGAPA in a thin film state, which was measured
by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki
Co., Ltd.) under air, was -5.47 eV. By the absorption edge obtained
from a Tauc plot of the absorption spectrum of the thin film, the
optical energy gap was estimated to be 2.55 eV, which means that
LUMO level of 2YGAPA is -2.92 eV.
Embodiment 12
In this embodiment, a synthetic method of
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (202), is
specifically described.
##STR00140##
[Step 1] Synthesis of 1-bromo-9,10-diphenylanthracene
(i) Synthesis of 1-bromo-9,10-anthraquinone
A synthetic scheme of 1-bromo-9,10-anthraquinone is shown in
(C-23).
##STR00141##
20.0 g (88.8 mmol) of 1-amino-9,10-anthraquinone, 36.7 g (164 mmol)
of copper bromide (II), and 240 mL of acetonitrile were put into a
500 mL three-neck flask, and the atmosphere of the flask was
substituted with nitrogen. Thereafter, 15.8 mL (133 mmol) of
tert-butyl nitrite was added, and the mixture was stirred for 6
hours at 65.degree. C. After the reaction was completed, the
reaction mixture was poured into 1.3 L of 3 mol/L hydrochloric
acid, which was followed by additional stirring for 3 hours at room
temperature. A precipitate in the mixture was collected by suction
filtration, and the precipitate was washed with water and then with
ethanol. Then, the obtained solid was dissolved in a mixed solvent
of toluene and chloroform, and the solution was subjected to
suction filtration through Florisil, celite, and then alumina. The
filtrate was concentrated, and the residue was purified by silica
gel column chromatography (eluent: toluene). The obtained solid was
recrystallized with a mixed solvent of chloroform and hexane,
giving 9.37 g of 1-bromo-9,10-anthraquinone as yellow powder in 36%
yield.
(ii) Synthesis of
1-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol
A synthetic scheme of
1-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol is shown in
(C-24).
##STR00142##
9.37 g (32.4 mmol) of 1-bromoanthraquinone was put into a 500 mL
three neck-flask, and the atmosphere of the flask was substituted
with nitrogen. 150 mL of tetrahydrofuran (abbreviation: THF) was
added to the flask, and then 34.0 mL (71.3 mmol) of phenyllithium
(2.1 mol/L dibutyl ether solution) was added in one portion. The
solution was stirred for 24 hours at room temperature. After the
reaction was completed, the reaction solution was washed with
water, and the aqueous layer was extracted with ethyl acetate. The
extracted part was combined with the organic layer, and then dried
with magnesium sulfate. After drying, the mixture was subjected to
suction filtration, and the filtrate was concentrated, resulting in
14.4 g of 1-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol as
a brown, oily compound in 100% yield.
(iii) Synthesis of 1-bromo-9,10-diphenylanthracene
A synthetic scheme of 1-bromo-9,10-diphenylanthracene is shown in
(C-5).
##STR00143##
14.4 g (32.4 mmol) of
1-bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9.68 g
(58.3 mmol) of potassium iodide, 18.6 g (175 mmol) of sodium
phosphinate monohydrate, and 100 mL of glacial acetic acid were put
into a 500 mL three-neck flask, and the mixture was refluxed for 5
hours at 120.degree. C. After the reaction was completed, 40 mL of
a 50% phosphinic acid was added to the mixture, and stirring was
kept for 18 hours at room temperature. After the reaction was
completed, the reaction solution was washed with water, and the
aqueous layer was extracted with ethyl acetate. The extracted part
was combined with the organic layer, and then dried with magnesium
sulfate. After drying, a mixture was subjected to suction
filtration, and the filtrate was concentrated. The obtained residue
was dissolved in toluene, and filtered through Florisil, celite,
and then alumina, and the filtrate was concentrated. The obtained
residue was purified by silica gel column chromatography (eluent;
toluene:hexane=1:5). The resulting solid was washed with ethanol,
providing 0.50 g of 1-bromo-9,10-diphenylanthracene as light yellow
powder in 3.8% yield.
[Step 2] Synthetic Method of 1PCAPA
A synthetic scheme of 1PCAPA is shown in (C-26).
##STR00144##
0.50 g (1.2 mmol) of 1-bromo-9,10-diphenylanthracene synthesized in
Step 1 of Embodiment 12, 0.45 g (1.3 mmol) of
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA),
0.035 g (0.061 mmol) of bis(dibenzylideneacetone)palladium (0), and
0.29 g (3.1 mmol) of sodium tert-butoxide were put into a 100 mL
three-neck flask, and the atmosphere of the flask was substituted
with nitrogen. Then, 10 mL of toluene and 0.12 g (0.061 mmol) of
tri(tert-butyl)phosphine (10% hexane solution) were added to the
flask, and the reaction mixture was stirred for 18 hours at
80.degree. C. After the reaction was completed, the reaction
mixture was diluted with toluene, and subjected to suction
filtration through. Florisil, celite, and then alumina, and then
the filtrate was concentrated. The obtained residue was purified by
silica gel column chromatography (eluent; hexane:toluene=3:2), and
the obtained solid was recrystallized with chloroform and hexane,
giving 0.08 g of the target compound as orange powder in 10% yield.
It was confirmed by a nuclear magnetic resonance measurement (NMR)
that this compound was
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=6.93-6.97 (m, 1H), 7.12-7.32 (m, 16H),
7.39-7.41 (m, 2H), 7.47-7.66 (m, 13H), 7.88-7.97 (m, 2H). The
.sup.1H NMR chart is shown in each of FIGS. 115A and 115B. Note
that the range of 6.5 ppm to 8.5 ppm in FIG. 115A is expanded and
shown in FIG. 115B.
The absorption spectrum of a toluene solution of 1PCAPA is shown in
FIG. 116. An ultraviolet-visible spectrophotometer (type V550,
manufactured by Japan Spectroscopy Corporation) was used for
measurement. The absorption spectrum of the solution is shown in
FIG. 116, which was obtained by subtracting the spectrum of the
quartz substrate from the raw spectra of the sample solution
charged in a quartz cell. In FIG. 116, a horizontal axis shows
wavelength (nm) and a vertical axis shows absorption intensity (an
arbitrary unit). In the case of the toluene solution, absorption
was observed at around 443 nm. Further, an emission spectrum of the
toluene solution (excitation wavelength of 430 nm) of 1PCAPA is
shown in FIG. 117. In FIG. 117, a horizontal axis shows wavelength
(nm) and a vertical axis shows emission intensity (an arbitrary
unit). In the case of the toluene solution, the maximum emission
wavelength was 512 nm (excitation wavelength of 430 nm).
Embodiment 13
In this embodiment, a synthetic method of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-
-yl)amino]anthracene (abbreviation: 2PCADFA), which is the
anthracene derivative of the present invention represented by
Structural Formula (207), is specifically described.
##STR00145##
[Step 1] Synthesis of 2-bromo-9,9-dimethylfluorene
(i) Synthesis of 2-bromo-9,9-dimethylfluorene
A synthetic scheme of 2-bromo-9,9-dimethylfluorene is shown in
(C-27).
##STR00146##
12.5 g (51 mmol) of 2-bromofluorene, 8.5 g (51 mmol) of potassium
iodide, 14.3 g (0.50 mol) of potassium hydroxide, and 250 mL of
dimethylsulfoxide were put into a 500 mL Erlenmeyer flask, and the
mixture was stirred for 30 minutes. 10 mL of methyl iodide was
slowly added to this mixture. This mixture was stirred for 48 hours
at room temperature. After the reaction, 400 mL of chloroform was
added to the reaction solution, and stirring was continued. This
solution was washed with 1N hydrochloric acid, saturated sodium
carbonate aqueous solution, and brine in this order. Then,
magnesium sulfate was added to the organic layer to dry the layer.
After drying, this mixture was subjected to suction filtration, and
concentrated, and the residue was subjected to the purification by
silica gel column chromatography. For the column chromatography,
hexane was used as an eluent first, and then a mixed solvent of
ethyl acetate:hexane=1:5 was used as a second eluent. The
corresponding fraction was concentrated and dried, resulting in 12
g of a brown, oily compound in 97% yield.
(ii) Synthesis of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromo-9,10-dihydroanthracene-9,10-d-
iol
A synthetic scheme of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromo-9,10-dihydroanthracene-9,10-d-
iol is shown in each of (C-28) and (C-29).
##STR00147##
##STR00148##
12 g (46 mmol) of 2-bromo-9,9-dimethylfluorene and 150 mL of
tetrahydrofuran (abbreviation: THF) were put into a 500 mL
three-neck flask, and the inside of the flask was substituted with
nitrogen. This solution was stirred for 20 minutes at -78.degree.
C. Then, 35 mL of an 1.6 mol/L hexane solution of n-butyllithium
was slowly dropwised into the solution, and stirring was conducted
for 1.5 hours at -78.degree. C. After the reaction, into the
reaction mixture was added 5.4 g (19 mmol) of
2-bromo-9,10-anthraquinone dissolved in 100 mL of THF. The
resulting solution was stirred for 18 hours at room temperature.
After stirring, to this solution was added 1N hydrochloric acid,
and the solution was stirred for 30 minutes. The reaction mixture
was transferred to a separating funnel, and an aqueous layer was
extracted with ethyl acetate. The extracted layer and the organic
layer were combined and washed with a saturated sodium bicarbonate
aqueous solution, and then with brine. After washing, magnesium
sulfate was added to the organic layer to dry the organic layer.
After drying, this mixture was subjected to suction filtration. The
obtained filtrate was subjected to suction filtration through
celite, Florisil and then alumna, and the filtrate obtained was
concentrated to give the title compound as a brown, oily
compound.
(iii) Synthesis of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromoanthracene
A synthetic scheme of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromoanthracene is shown in
(C-30).
##STR00149##
A solution of 46 mmol of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromo-9,10-dihydroanthracene-9,10-d-
iol, 24 g (0.23 mol) of sodium phosphinate monohydrate, and 15 g
(91 mmol) of potassium iodide in 100 mL of glacial acetic acid was
stirred for 4 hours at 120.degree. C. After the reaction, 60 mL of
a 50% phosphinic acid was added to the reaction mixture, and then
stirring was kept for additional 2 hours at 120.degree. C. Water
was added to the mixture, and the mixture was stirred for 1 hour.
After the mixture was filtered, the resulting solid was washed with
water and dissolved in toluene, and the toluene-solution was washed
with a saturated sodium bicarbonate aqueous solution and brine.
Magnesium sulfate was added to this organic layer to dry the
organic layer. This mixture was subjected to suction filtration,
and the filtrate was filtered through celite, Florisil, and then
alumina. The filtrate was concentrated, and the resulting solid was
dissolved in a mixed solvent of chloroform and methanol, which was
followed by irradiating ultrasound to yield 14 g of the title
compound as a light yellow solid. Total yield of the steps of (ii)
and (iii) was 47%.
[Step 2] Synthesis of 2PCADFA
A synthetic scheme of 2PCADFA is shown in (C-31).
##STR00150##
1.5 g (2.3 mmol) of
9,10-bis(9,9-dimethylfluorene-2-yl)-2-bromoanthracene, 1.0 g (10
mmol) of sodium tert-butoxide, 0.78 g (2.3 mmol)
N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA), and
0.08 g (0.16 mmol) of bis(dibenzylideneacetone)palladium (0) were
put into a 100 mL three-neck flask, and the inside of the flask was
substituted with nitrogen. 30 mL of toluene and 0.05 mL of a 10%
hexane solution of tri(tert-butyl)phosphine were added to this
mixture, and this mixture was heated and stirred for 5 hours at
80.degree. C. After stirring, toluene was added to the reaction
mixture, and this suspension was washed with a saturated sodium
bicarbonate aqueous solution and brine. The organic layer was
subjected to suction filtration through Florisil, celite, and then
alumina, washed with water and then with brine, and dried over
magnesium sulfate. This mixture was subjected to suction filtration
to remove magnesium sulfate, and the obtained filtrate was
concentrated. The resulting solid was purified by silica gel column
chromatography (eluent; toluene:hexane=1:9, then
toluene:hexane=1:5, and then toluene:hexane=1:2). The obtained
solid was recrystallized with a mixed solvent of dichloromethane
and hexane, giving 0.70 g yellow powder in 77% yield. It was
confirmed by nuclear magnetic resonance measurement (NMR) that this
compound was
9,10-bis(9,9-dimethylfluorene-2-yl)-2-[N-phenyl-N-(9-phenyl-9H-carbazol-3-
-yl)amino]anthracene (abbreviation: 2PCADFA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, CDCl.sub.3): .delta.=1.04 (d, J=1.95, 3H), 1.41 (s, 3H),
1.54-1.59 (m, 6H), 6.83-6.90 (m, 1H), 7.09-7.24 (m, 10H), 7.25-7.64
(m, 20H), 7.63-7.70 (m, 2H), 7.70-7.75 (m, 1H), 7.82 (dd, J=2.0,
6.8 Hz, 1H), 7.88 (s, 1H), 7.92 (d, J=8.3 Hz, 2H). The .sup.1H NMR
chart is shown in each of FIGS. 118A and 118B. Note that the range
of 6.5 ppm to 8.5 ppm in FIG. 118A is expanded and shown in FIG.
118B.
Sublimation purification of 0.70 g of the obtained yellow solid was
carried out by a train sublimation method. The sublimation
purification was carried out under reduced pressure of 7.0 Pa, with
a flow rate of argon at 3 mL/min, at 352.degree. C. for 15 hours.
0.62 g of the compound was recovered, which corresponds to the
yield of 89%.
The absorption spectrum of a toluene solution of 2PCADFA is shown
in FIG. 119. An ultraviolet-visible spectrophotometer (type V550,
manufactured by Japan Spectroscopy Corporation) was used for
measurement. The absorption spectrum of the solution is shown in
FIG. 119, which was obtained by subtracting the spectrum of the
quartz substrate from the raw spectra of the sample solution
charged in a quartz cell. In FIG. 119, a horizontal axis shows
wavelength (nm) and a vertical axis shows absorption intensity (an
arbitrary unit). In the case of the toluene solution, absorption
was observed at around 442 nm. Further, an emission spectrum of the
toluene solution (excitation wavelength of 430 nm) of 2PCADFA is
shown in FIG. 119. In FIG. 119, a horizontal axis shows wavelength
(nm) and a vertical axis shows emission intensity (an arbitrary
unit). In the case of the toluene solution, the maximum light
emission wavelength was 516 nm (excitation wavelength of 439
nm).
Embodiment 14
In this embodiment, a synthetic method of
9,10-diphenyl-2-[N-(4'-diphenylamino-1,1'-biphenyl-4-yl)-N-phenylamino]an-
thracene (abbreviation: 2DPBAPA), which is the anthracene
derivative of the present invention represented by Structural
Formula (119), is specifically described. Note that 2DPBAPA
represented by Structural Formula (119) corresponds to the case
where Ar.sup.1 and Ar.sup.2 in General Formula (5) are each
Structural Formula (20-1), and A is Structural formula (31-18).
##STR00151##
[Step 1] Synthesis of triphenylamine-4-boronic acid
A synthetic scheme of triphenylamine-4-boronic acid is shown in
(C-32).
##STR00152##
Under nitrogen, into a solution of 10 g (31 mmol) of
4-bromotriphenylamine in tetrahydrofuran (THF, 150 mL) was added 20
mL (32 mmol) of n-butyllithium (1.58 mol/L hexane solution) with a
syringe at -80.degree. C., which was followed by stirring for 1 h
at the same temperature. After adding 3.8 mL (34 mmol) of trimethyl
borate to this solution, stirring was kept allowing the temperature
of the solution to gradually rise to room temperature for about 15
hours. About 150 mL of diluted hydrochloric acid (1.0 mol/L) was
added to this solution, and the solution was stirred for 1 hour.
The aqueous layer of this mixture was extracted with ethyl acetate,
and the extracted solution and the organic layer were combined and
washed with a saturated sodium bicarbonate aqueous solution.
Thereafter, the organic layer was dried with magnesium sulfate,
filtered, and concentrated to give a light brown, oily compound.
This oily compound was dissolved in 20 mL of chloroform, and then
about 50 mL of hexane was added to the solution. A white solid was
precipitated after keeping 1 hour, which was followed by
filtration, giving 5.2 g of the target compound as a white solid in
58% yield.
[Step 2] Synthesis of N,N',N'-triphenylbenzidine (abbreviation:
DPAB)
A synthetic scheme of N,N',N'-triphenylbenzidine (abbreviation:
DPAB) is shown in (C-33).
##STR00153##
4.3 g (17 mmol) of 4-bromodiphenylamine, 5 g (17 mmol) of
triphenylamine-4-boronic acid, and 532 mg (1.8 mmol) of
tri(o-tolyl)phosphine were put into a 500 mL three-neck flask, and
the inside of the flask was substituted with nitrogen. Then, 60 mL
of toluene, 40 mL of ethanol, and 14 mL of potassium carbonate
aqueous solution (0.2 mol/L) were added to this mixture. After this
mixture was degassed under reduced pressure while being stirred, 75
mg (0.35 mmol) of palladium acetate (II) was added. This mixture
was refluxed for 10.5 hours at 100.degree. C. The aqueous layer of
this mixture was extracted with toluene. This extracted solution
and the organic layer were combined, washed with brine, dried with
magnesium sulfate, filtered, and concentrated, which resulted in a
light brown, oily compound. This oily compound was dissolved in
about 50 mL of toluene, and then subjected to suction filtration
through celite, alumina, and Florisil. The filtrate was
concentrated, and the residue was purified by silica gel column
chromatography (eluent; hexane:toluene=4:6) to give a white solid
which was then recrystallized with chloroform/hexane to afford 3.5
g of the target compound as a white solid in 49% yield.
[Step 3] Synthesis of 2DPBAPA
A synthetic scheme of 2DPBAPA is shown in (C-34).
##STR00154##
1.5 g (3.6 mmol) of 2-bromo-9,10-diphenylanthracene, 1.5 g (3.6
mmol) of N,N',N'-triphenylbenzidine (abbreviation: DPAB), and 1.5 g
(16 mmol) of sodium tert-butoxide were put into a 100 mL three-neck
flask, and the inside of the flask was substituted with nitrogen.
20 mL of toluene and 0.10 mL of tri(tert-butyl)phosphine (10 wt %
hexane solution) were added to this mixture. After this mixture was
degassed under reduced pressure while being stirred, 41 mg (0.072
mmol) of bis(dibenzylideneacetone)palladium (0) was added. Then,
the mixture was stirred for 3 hours at 100.degree. C. After about
50 mL of toluene was added to the reaction mixture, this mixture
was subjected to suction filtration through celite, Florisil, and
alumina. The obtained filtrate was concentrated, yielding oily
compound. About 10 mL of toluene was added to this oily compound,
which was left for about 2 hours to afford a yellow solid as a
precipitate. Suction filtration of this precipitate gave 2.5 g of
the target compound as yellow powder in 91% yield. By a nuclear
magnetic resonance measurement (NMR), it was confirmed that this
compound was
9,10-diphenyl-2-[N(4'-diphenylamino-1,1'-biphenyl-4-yl)-N-phenylamino]ant-
hracene (abbreviation: 2DPBAPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, DMSO-d.sub.6): .delta.=7.01-7.08 (m, 11H), 7.13-7.17 (m, 5H),
7.22-7.89 (m, 12H), 7.42-7.66 (m, 12H). The .sup.1H NMR chart is
shown in each of FIGS. 120A and 120B. Note that the range of 6.5
ppm to 8.5 ppm in FIG. 120A is expanded and shown in FIG. 120B.
The absorption spectrum of a toluene solution of 2DPBAPA is shown
in FIG. 121. An ultraviolet-visible spectrophotometer (type V550,
manufactured by Japan Spectroscopy Corporation) was used for
measurement. The absorption spectrum of the solution is shown in
FIG. 121, which was obtained by subtracting the spectrum of the
quartz substrate from the raw spectra of the sample solution
charged in a quartz cell. In FIG. 121, a horizontal axis shows
wavelength (nm) and a vertical axis shows absorption intensity (an
arbitrary unit). In the case of the toluene solution, absorption
was observed at around 355 nm. Further, an emission spectrum of the
toluene solution (excitation wavelength of 370 nm) of 2DPBAPA is
shown in FIG. 122. In FIG. 122, a horizontal axis shows wavelength
(nm) and a vertical axis shows emission intensity (an arbitrary
unit). In the case of the toluene solution, the maximum emission
wavelength was 493 nm (excitation wavelength of 370 nm).
Embodiment 15
In this embodiment, a synthetic method of
2-{N-[4'-(9H-carbazol-9-yl)-1,1'-biphenyl-4-yl]-N-phenylamino}-9,10-diphe-
nylanthracene (abbreviation: 2YGBAPA), which is the anthracene
derivative of the present invention represented by Structural
Formula (319), is specifically described. Note that 2YGBAPA
represented by Structural Formula (319) corresponds to the case
where Ar.sup.1 and Ar.sup.2 in General Formula (5) are each
Structural Formula (20-1), and A is Structural formula (33-10).
##STR00155##
[Step 1] Synthesis of 9-phenylcarbazole-3-ylboronic acid
A synthetic scheme of 9-phenylcarbazole-3-ylboronic acid is shown
in (C-35).
##STR00156##
Into a solution of 19.6 g (60.7 mmol) of 3-bromo-9-phenylcarbazole,
prepared in Step 1 of the Embodiment 2, in THF (100 mL) was added
dropwise 66.8 mL (42.3 mmol) of an n-butyllithium hexane solution
(1.58 mol/L) at -78.degree. C. under nitrogen, which was followed
by stirring for 3 hours at the same temperature. Thereafter, 13.5
mL (140 mmol) of trimethyl borate was added, and stirring was
continued for 24 hours while gradually raising the reaction
temperature to room temperature. 200 mL of 2.0 mol/L hydrochloric
acid was added to the solution, and additional stirring was
conducted for 1 hour at room temperature. After the solution was
extracted with ethyl acetate, the organic layer was washed with
brine, dried with magnesium sulfate, filtered, and concentrated.
The resulting solid was recrystallized with a mixed solvent of
chloroform and hexane, giving 10.2 g of
9-phenylcarbazole-3-ylboronic acid as white powder in 58%
yield.
[Step 2] Synthesis of 4-[4(9H-carbazol-9-yl)phenyl]diphenylamine
(abbreviation: YGBA).
A synthetic scheme of 4-[4(9H-carbazol-9-yl)phenyl]diphenylamine
(abbreviation: YGBA) is shown in (C-36).
##STR00157##
2.2 g (8.8 mmol) of 4-bromodiphenylamine, 2.5 g (8.8 mmol) of
triphenylamine-4-boronic acid, and 398 mg (1.3 mmol) of
tri(o-tolyl)phosphine were put into a 200 mL three-neck flask, and
the inside of the flask was substituted with nitrogen. 30 mL of
toluene, 20 mL of ethanol, and 14 mL of potassium carbonate aqueous
solution (0.2 mol/L) were added to this mixture. This mixture was
degassed under reduced pressure while being stirred, and 59 mg
(0.26 mmol) of palladium acetate (II) was added. This mixture was
refluxed for 6.5 hours at 100.degree. C. After this mixture was
left to cool for about 15 hours, a light blackish-brown solid was
precipitated. This solid was collected by suction filtration, and
2.5 g of the target compound was obtained as light blackish-brown
solid in 70% yield.
[Step 3] Synthesis of 2YGBAPA
A synthetic scheme of 2YGBAPA is shown in (C-37).
##STR00158##
1.2 g (3.0 mmol) of 2-bromo-9,10-diphenylanthracene, 1.2 g (3.0
mmol) of YGBA, and 1.5 g (16 mmol) of sodium tert-butoxide were put
into a 100 mL three-neck flask, and the inside of the flask was
charged with nitrogen. 15 mL of toluene and 0.20 mL of
tri(tert-butyl)phosphine (10 wt % hexane solution) were added to
this mixture. This mixture was degassed under reduced pressure
while being stirred, and 86 mg (0.15 mmol) of
bis(dibenzylideneacetone)palladium (0) was added. Thereafter, this
mixture was stirred for 3 hours at 100.degree. C. This mixture was
subjected to suction filtration through celite, alumina, and
Florisil. An oily compound obtained by concentrating the obtained
filtrate was purified by silica gel column chromatography (eluent
was hexane:toluene=7:3), and the resulting yellow solid was
recrystallized with chloroform/methanol, giving 462 g of the target
compound as a yellow solid in 21% yield. By a nuclear magnetic
resonance measurement (NMR), it was confirmed that this compound
was
2-{N-[4'-(9H-carbazol-9-yl)-1,1'-biphenyl-4-yl]-N-phenylamino}-9,10-diphe-
nylanthracene (abbreviation: 2YGBAPA).
.sup.1H NMR data of this compound is shown below. .sup.1H NMR (300
MHz, DMSO-d.sub.6): .delta.=7.08-7.14 (m, 5H), 7.20 (dd, J=2.4, 9.5
Hz, 1H), 7.28-7.61 (m, 22H), 7.64 (d, J=7.2 Hz, 2H), 7.70 (dd,
J=2.4, 7.7 Hz, 4H), 7.91 (d, J=8.4 Hz, 2H), 8.26 (d, J=7.8 Hz, 2H).
The .sup.1H NMR chart is shown in each of FIGS. 123A and 123B. Note
that the range of 6.5 ppm to 9.0 ppm in FIG. 123A is expanded and
shown in FIG. 123B.
The absorption spectrum of a toluene solution of 2YGBAPA is shown
in FIG. 124. An ultraviolet-visible spectrophotometer (type V550,
manufactured by Japan Spectroscopy Corporation) was used for
measurement. The absorption spectrum of the solution is shown in
FIG. 124, which was obtained by subtracting the spectrum of the
quartz substrate from the raw spectra of the sample solution
located in a quartz cell. In FIG. 124, a horizontal axis shows
wavelength (nm) and a vertical axis shows absorption intensity (an
arbitrary unit). In the case of the toluene solution, absorption
was observed at around 344 nm. Further, an emission spectrum of the
toluene solution (excitation wavelength of 370 nm) of 2YGBAPA is
shown in FIG. 125. In FIG. 125, a horizontal axis shows wavelength
(nm) and a vertical axis shows emission intensity (an arbitrary
unit). In the case of the toluene solution, the maximum light
emission wavelength was 485 nm (excitation wavelength of 370
nm).
Embodiment 16
In this embodiment, a light-emitting element of the present
invention is described with reference to FIG. 10.
A manufacturing method of a light-emitting element of this
embodiment is described below.
First, a film of indium tin oxide containing silicon oxide (ITSO)
was formed by sputtering over the glass substrate 2101 to form the
first electrode 2102. Note that the film thickness of the first
electrode 2102 was 110 nm, and the area of the electrode was 2
mm.times.2 mm.
Next, the substrate over which the first electrode was formed was
fixed to a substrate holder provided in a vacuum evaporation
apparatus, so that a surface over which the first electrode was
formed faced down. Then, after reducing pressure of the vacuum
evaporation apparatus to about 10.sup.-4 Pa, the layer 2103
containing a composite material, which contains an organic compound
and an inorganic compound, was formed over the first electrode 2102
by co-evaporating 4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl
(abbreviation: NPB) and molybdenum oxide (VI). The film thickness
was to be 50 nm, and a ratio of NPB and molybdenum oxide (VI) was
adjusted to be 4:1 (=NPB:molybdenum oxide) in weight ratio.
Subsequently, a film of
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
was formed over the layer 2103 containing a composite material to
have a thickness of 10 nm by the evaporation method using
resistance heating system, thereby forming the hole transporting
layer 2104.
Further, by co-evaporating
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA)
and
2-{N-[4-(carbazol-9-yl)phenyl]-N-phenylamino}-9,10-diphenylanthracene
(abbreviation: 2YGAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (301), the
light-emitting layer 2105 with a thickness of 30 nm was formed over
the hole transporting layer 2104. Here, a rate of evaporation was
adjusted so that the weight ratio of CzPA and 2YGAPA was 1:0.05
(=CzPA: 2YGAPA).
Thereafter, the electron transporting layer 2106 was formed over
the light-emitting layer 2105 by forming a film of
tris(8-quinolinolato)aluminum (abbreviation: Alq) to have a film
thickness of 10 nm by means of the evaporation using resistance
heating system.
Further, the electron injecting layer 2107 was formed at a
thickness of 20 nm over the electron transporting layer 2106 by
co-evaporating tris(8-quinolinolato)aluminum (abbreviation: Alq)
and lithium (Li). Here, the rate of evaporation was adjusted so
that the weight ratio of Alq and Li was 1:0.01 (=Alq:Li).
Finally, by forming a film of aluminum as the second electrode 2108
with a film thickness of 200 nm over the electron injecting layer
2107 using the evaporation method by resistance heating system, a
light-emitting element 12 was fabricated.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 13 are shown in FIGS. 126, 127, and
128, respectively. Also, the emission spectrum which was obtained
at a current of 1 mA is illustrated in FIG. 129. Further, FIGS. 130
and 131 demonstrate time dependence of normalized luminance and
time dependence of operation voltage, respectively, of the
light-emitting element 13 when initial luminance was 1000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 13 at luminance of 1000 cd/m.sup.2 was (x=0.21, y=0.51),
and light emission was blue green. Current efficiency at luminance
of 1000 cd/m.sup.2 was 9.6 cd/A, meaning that high current
efficiency was exhibited. In addition, as shown in FIG. 129,
maximum emission wavelength at a current of 1 mA was 489 nm. It can
be concluded from FIG. 130 that the light-emitting element 13 has a
long lifetime, since 82% of the initial luminance was maintained
even after 640 hours.
Embodiment 17
In this embodiment, a light-emitting element of the present
invention is described with reference to FIG. 10.
Hereinafter, a manufacturing method of a light-emitting element of
this embodiment is shown.
First, a film of indium tin oxide containing silicon oxide (ITSO)
was formed by sputtering over the glass substrate 2101 to form the
first electrode 2102. Note that the film thickness of the first
electrode 2102 was 110 nm, and the area of the electrode was 2
mm.times.2 mm.
Next, the substrate over which the first electrode was formed was
fixed to a substrate holder provided in a vacuum evaporation
apparatus, so that a surface over which the first electrode was
formed faced down. Then, after reducing pressure of the vacuum
evaporation apparatus to about 10.sup.-4 Pa, the layer 2103
containing a composite material, which contains an organic compound
and an inorganic compound, was formed over the first electrode 2102
by co-evaporating 4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl
(abbreviation: NPB) and molybdenum oxide (VI). The film thickness
was to be 50 nm, and a ratio of NPB and molybdenum oxide (VI) was
adjusted to be 4:1 (=NPB:molybdenum oxide) in weight ratio.
Subsequently, a film of
4,4'-bis[N-(1-napthyl)-N-phenylamino]biphenyl (abbreviation: NPB)
was formed over the layer 2103 containing, a composite material to
have a thickness of 10 nm by the evaporation method using
resistance heating system, thereby forming the hole transporting
layer 2104.
Further, by co-evaporating
9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA)
and
9,10-diphenyl-1-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]anthracene
(abbreviation: 1PCAPA), which is the anthracene derivative of the
present invention represented by Structural Formula (202), the
light-emitting layer 2105 with a thickness of 40 nm was formed over
the hole transporting layer 2104. Here, a rate of evaporation was
adjusted so that the weight ratio of CzPA and 1PCAPA was 1:0.05
(=CzPA: 1PCAPA).
Thereafter, as to the light-emitting element 14, the electron
transporting layer 2106 was formed over the light-emitting layer
2105 by fabricating a film of tris(8-quinolinolato)aluminum
(abbreviation: Alq) with a film thickness of 30 nm by means of the
evaporation method using resistance heating system. As to the
light-emitting element 15, a film of bathophenanthroline
(abbreviation: BPhen) was formed with a thickness of 30 nm to form
the electron transporting layer 2106.
Furthermore, a film of lithium fluoride (LiF) was formed over the
electron transporting layer 2106 to have a thickness of 1 nm, to
form an electron injecting layer 2107.
Finally, by forming a film of aluminum as the second electrode 2108
with a film thickness of 200 nm over the electron injecting layer
2107 using the evaporation method by resistance heating system,
light-emitting elements 14 and 15 were fabricated.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 14 are shown in FIGS. 132, 133, and
134, respectively. Also, the emission spectrum which was obtained
at a current of 1 mA is illustrated in FIG. 135. Further, FIGS. 136
and 137 demonstrate time dependence of normalized luminance and
time dependence of operation voltage, respectively, of the
light-emitting element 14 when initial luminance was 3000
cd/m.sup.2. A CIE chromaticity coordinate of the light-emitting
element 14 at luminance of 3000 cd/m.sup.2 was (x=0.31, y=0.61),
and light emission was green. Current efficiency at luminance of
3000 cd/m.sup.2 was 13.9 cd/A, meaning that high current efficiency
was exhibited. In addition, as shown in FIG. 135, maximum emission
wavelength at a current of 1 mA was 515 nm. It can be concluded
from FIG. 136 that the light-emitting element 14 has a long
lifetime, since 74% of the initial luminance was maintained even
after 500 hours.
A current density-luminance characteristic, a voltage-luminance
characteristic, and a luminance-current efficiency characteristic
of the light-emitting element 15 are shown in FIGS. 138, 139, and
140, respectively. Also, the emission spectrum which was obtained
at a current of 1 mA is illustrated in FIG. 141. A CIE chromaticity
coordinate of the light-emitting element 15 at luminance of 3000
cd/m.sup.2 was (x=0.32, y=0.59), and light emission was green.
Current efficiency at luminance of 3000 cd/m.sup.2 was 15.9 cd/A,
meaning that high current efficiency was exhibited. Power
efficiency at luminance of 3000 cd/m.sup.2 was 16.7 lm/W,
indicating that the element 15 can be operated at low power
consumption. In addition, as shown in FIG. 141, maximum emission
wavelength at a current of 1 mA was 515 nm.
This application is based on Japanese Patent Application serial no.
2006-127118 filed on Apr. 28, 2006 and Japanese Patent Application
serial no. 2006-233244 filed on Aug. 30, 2006 in Japan Patent
Office, the entire contents of which are hereby incorporated by
reference.
* * * * *